WO2014032616A1 - Improved low temperature impact properties in pc-siloxane copolymer blend with black and white color capability - Google Patents

Improved low temperature impact properties in pc-siloxane copolymer blend with black and white color capability Download PDF

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Publication number
WO2014032616A1
WO2014032616A1 PCT/CN2013/082706 CN2013082706W WO2014032616A1 WO 2014032616 A1 WO2014032616 A1 WO 2014032616A1 CN 2013082706 W CN2013082706 W CN 2013082706W WO 2014032616 A1 WO2014032616 A1 WO 2014032616A1
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Prior art keywords
polycarbonate
polysiloxane
composition
polycarbonate copolymer
copolymer
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PCT/CN2013/082706
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French (fr)
Inventor
Jian Yang
Robert Dirk Van De Grampel
Mark Adrianus Johannes van der Mee
Jon Michael Malinoski
Niles Richard Rosenquist
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Sabic Innovative Plastics Ip B.V.
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Priority to US14/425,193 priority Critical patent/US9587109B2/en
Priority to EP13832089.0A priority patent/EP2890743B1/en
Priority to CN201380045582.9A priority patent/CN104583320B/en
Priority to KR1020157008162A priority patent/KR101572068B1/en
Publication of WO2014032616A1 publication Critical patent/WO2014032616A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/38Polysiloxanes modified by chemical after-treatment
    • C08G77/382Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42Block-or graft-polymers containing polysiloxane sequences
    • C08G77/445Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
    • C08G77/448Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10Block- or graft-copolymers containing polysiloxane sequences
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2237Oxides; Hydroxides of metals of titanium
    • C08K2003/2241Titanium dioxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • compositions that generally comprise a blend a polycarbonate polymer with a first polysiloxane-polycarbonate copolymer, a second polysiloxane-polycarbonate copolymer, and a color composition.
  • the present disclosure describes a composition with a constant percentage of siloxane in the formulations.
  • the composition achieves improved impact properties, as well as the ability to achieve deep black and bright white colors.
  • the present disclosure describes a polycarbonate blend composition
  • a polycarbonate blend composition comprising: (a) a polycarbonate homopolymer; (b) a first polysiloxane-polycarbonate copolymer comprising: (i) polydiorganosiloxane blocks comprising repeating structural units of formula:
  • polydiorganosiloxane block length (E) is from 30 to 60; and (ii) polycarbonate blocks comprising polycarbonate units of formula: O
  • polydiorganosiloxane blocks comprising repeating structural units of formula:
  • polydiorganosiloxane block length (E) is from 30 to 100; and (ii) polycarbonate blocks comprising polycarbonate units of formula:
  • the blend composition has an average melt flow rate (MFR) of 7 or greater measured at 300 °C/1.2 kg; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has a black color characterized by an average L* value of 27 or less as measured by the CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -30 °C of 650 J/m or greater and a % ductility of 100% according to ASTM D256-2010.
  • MFR average melt flow rate
  • compositions that have an improved notched Izod impact strength that does not comprise the other properties of the composition.
  • articles comprising the disclosed composition, for example an article as a component in a smart phone.
  • the invention relates to methods of making the disclosed compositions.
  • reference to a filler includes mixtures of fillers.
  • Ranges can be expressed herein as from “about” one particular value, and/or to "about” another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as "about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10" is also disclosed. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.
  • the terms "about” and “at or about” mean that the amount or value in question can be the value designated some other value approximately or about the same. It is generally understood, as used herein, that it is the nominal value indicated ⁇ 10% variation unless otherwise indicated or inferred. The term is intended to convey that similar values promote equivalent results or effects recited in the claims. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but can be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art.
  • an amount, size, formulation, parameter or other quantity or characteristic is “about” or “approximate” whether or not expressly stated to be such. It is understood that where "about” is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.
  • condition effective to refers to such amount or condition that is capable of performing the function or property for which an effective amount is expressed. As will be pointed out below, the exact amount or particular condition required will vary from one aspect to another, depending on recognized variables such as the materials employed and the processing conditions observed. Thus, it is not always possible to specify an exact “effective amount” or “condition effective to.” However, it should be understood that an appropriate effective amount will be readily determined by one of ordinary skill in the art using only routine experimentation.
  • compositions of the invention Disclosed are the components to be used to prepare disclosed compositions of the invention as well as the compositions themselves to be used within methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds cannot be explicitly disclosed, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed and a number of modifications that can be made to a number of molecules including the compounds are discussed, specifically contemplated is each and every combination and permutation of the compound and the modifications that are possible unless specifically indicated to the contrary.
  • X and Y are present at a weight ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the compound.
  • weight percent As used herein the terms "weight percent,” “wt%,” and “wt. %,” which can be used interchangeably, indicate the percent by weight of a given component based on the total weight of the composition, unless otherwise specified. That is, unless otherwise specified, all wt% values are based on the total weight of the composition. It should be understood that the sum of wt% values for all components in a disclosed composition or formulation are equal to 100.
  • a weight percent of a component is based on the total weight of the formulation or composition in which the component is included. For example if a particular element or component in a composition or article is said to have 8% weight, it is understood that this percentage is relation to a total
  • compositional percentage of 100%
  • alkyl group as used herein is a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like.
  • a "lower alkyl” group is an alkyl group containing from one to six carbon atoms.
  • alkoxy as used herein is an alkyl group bound through a single, terminal ether linkage; that is, an “alkoxy” group can be defined as OR where R is alkyl as defined above.
  • a "lower alkoxy” group is an alkoxy group containing from one to six carbon atoms.
  • alkenyl group as used herein is a hydrocarbon group of from 2 to 24 carbon atoms and structural formula containing at least one carbon-carbon double bond.
  • alkynyl group as used herein is a hydrocarbon group of 2 to 24 carbon atoms and a structural formula containing at least one carbon-carbon triple bond.
  • aryl group as used herein is any carbon-based aromatic group including, but not limited to, benzene, naphthalene, etc.
  • aromatic also includes “heteroaryl group,” which is defined as an aromatic group that has at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus.
  • the aryl group can be substituted or unsubstituted.
  • the aryl group can be substituted with one or more groups including, but not limited to, alkyl, alkynyl, alkenyl, aryl, halide, nitro, amino, ester, ketone, aldehyde, hydroxy, carboxylic acid, or alkoxy.
  • cycloalkyl group is a non-aromatic carbon-based ring composed of at least three carbon atoms.
  • examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
  • heterocycloalkyl group is a cycloalkyl group as defined above where at least one of the carbon atoms of the ring is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulphur, or phosphorus.
  • aralkyl as used herein is an aryl group having an alkyl, alkynyl, or alkenyl group as defined above attached to the aromatic group.
  • An example of an aralkyl group is a benzyl group.
  • hydroxyalkyl group as used herein is an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group described above that has at least one hydrogen atom substituted with a hydroxyl group.
  • alkoxyalkyl group is defined as an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group described above that has at least one hydrogen atom substituted with an alkoxy group described above.
  • esters as used herein is represented by the formula— C(0)OA, where A can be an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl,
  • carbonate group as used herein is represented by the formula
  • R can be hydrogen, an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group described above.
  • aldehyde as used herein is represented by the formula -C(0)H.
  • keto group as used herein is represented by the formula -C(0)R, where R is an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group described above.
  • ether as used herein is represented by the formula AOA1 , where A and Al can be, independently, an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.
  • organic residue defines a carbon containing residue, i.e., a residue comprising at least one carbon atom, and includes but is not limited to the carbon-containing groups, residues, or radicals defined hereinabove.
  • Organic residues can contain various heteroatoms, or be bonded to another molecule through a heteroatom, including oxygen, nitrogen, sulfur, phosphorus, or the like. Examples of organic residues include but are not limited alkyl or substituted alkyls, alkoxy or substituted alkoxy, mono or di-substituted amino, amide groups, etc.
  • Organic residues can preferably comprise 1 to 18 carbon atoms, 1 to 15, carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms.
  • an organic residue can comprise 2 to 18 carbon atoms, 2 to 15, carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, 2 to 4 carbon atoms, or 2 to 4 carbon atoms.
  • a very close synonym of the term “residue” is the term "radical,” which as used in the specification and concluding claims, refers to a fragment, group, or substructure of a molecule described herein, regardless of how the molecule is prepared.
  • 2,4-dihydroxyphenyl radical in a particular compound has the structure
  • radical for example an alkyl
  • substituted alkyl can be further modified (i.e., substituted alkyl) by having bonded thereto one or more "substituent radicals.”
  • the number of atoms in a given radical is not critical to the present invention unless it is indicated to the contrary elsewhere herein.
  • Organic radicals contain one or more carbon atoms.
  • An organic radical can have, for example, 1-26 carbon atoms, 1-18 carbon atoms, 1-12 carbon atoms, 1-8 carbon atoms, 1-6 carbon atoms, or 1-4 carbon atoms.
  • an organic radical can have 2-26 carbon atoms, 2-18 carbon atoms, 2-12 carbon atoms, 2-8 carbon atoms, 2-6 carbon atoms, or 2-4 carbon atoms.
  • Organic radicals often have hydrogen bound to at least some of the carbon atoms of the organic radical.
  • One example, of an organic radical that comprises no inorganic atoms is a 5, 6, 7,
  • an organic radical can contain 1-10 inorganic heteroatoms bound thereto or therein, including halogens, oxygen, sulfur, nitrogen, phosphorus, and the like.
  • organic radicals include but are not limited to an alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, mono-substituted amino, di-substituted amino, acyloxy, cyano, carboxy, carboalkoxy, alkylcarboxamide, substituted alkylcarboxamide, dialkylcarboxamide, substituted dialkylcarboxamide, alkylsulfonyl, alkylsulfmyl, thioalkyl, thiohaloalkyl, alkoxy, substituted alkoxy, haloalkyl, haloalkoxy, aryl, substituted aryl, heteroaryl, heterocyclic, or substituted heterocyclic radicals, where
  • number average molecular weight or “M n” can be used interchangeably, and refer to the statistical average molecular weight of all the polymer chains in the sample and is defined by the formula:
  • M n can be determined for polymers, e.g., polycarbonate polymers, by methods well known to a person having ordinary skill in the art using molecular weight standards, e.g. polycarbonate standards or polystyrene standards, preferably certified or traceable molecular weight standards.
  • weight average molecular weight or “Mw” can be used interchangeably, and are defined by the formula:
  • M is the molecular weight of a chain and Ni is the number of chains of that molecular weight.
  • M w takes into account the molecular weight of a given chain in determining contributions to the molecular weight average.
  • M w can be determined for polymers, e.g. polycarbonate polymers, by methods well known to a person having ordinary skill in the art using molecular weight standards, e.g. polycarbonate standards or polystyrene standards, preferably certified or traceable molecular weight standards.
  • the PDI has a value equal to or greater than 1 , but as the polymer chains approach uniform chain length, the PDI approaches unity.
  • BisA can also be referred to by the name 4,4'-(propane-2,2-diyl)diphenol;
  • polycarbonate refers to an oligomer or polymer comprising residues of one or more dihydroxy compounds, e.g., dihydroxy aromatic compounds, joined by carbonate linkages; it also encompasses homopolycarbonates, copolycarbonates, and (co)polyester carbonates.
  • compositions disclosed herein have certain functions. Disclosed herein are certain structural requirements for performing the disclosed functions, and it is understood that there are a variety of structures that can perform the same function that are related to the disclosed structures, and that these structures will typically achieve the same result.
  • polycarbonate blend compositions generally comprising a polycarbonate polymer, a first
  • polysiloxane -polycarbonate copolymer a polysiloxane-polycarbonate copolymer
  • a second polysiloxane-polycarbonate copolymer a polysiloxane-polycarbonate copolymer
  • a colorant composition a colorant composition.
  • the polycarbonate-siloxane blends achieve improved impact properties, as well as the ability to achieve deep black and bright white colors.
  • the present disclosure utilizes a first and a second polycarbonate-polysiloxane copolymer which offers good impact properties compared to standard polycarbonates, wherein the first polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 4 to 8 wt % diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer; and wherein the second polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 1 to 30 wt % diorganosiloxane based on the total weight of the second polysiloxane-polycarbonate copolymer.
  • the second polysiloxane-polycarbonate copolymer is an opaque polycarbonate-polysiloxane copolymer which offers improved impact properties, but is unable to achieve the deep black colors due to the opacity of this copolymer.
  • a blend of both polycarbonate-polysiloxane copolymers, along with a polycarbonate and a colorant composition allows for improved impact properties while maintaining a constant formulation percentage of siloxane. Plus, the blend of both polycarbonate-polysiloxane copolymers, along with a polycarbonate and a colorant composition, allows for the ability to achieve deep black and bright white colors.
  • the relative low color (YI ⁇ 10 at 3.2 mm thickness) and high transparency (percent haze ⁇ 3.0 at 3.2 mm thickness) give the blend the ability to achieve deep black and bright white colors.
  • the present disclosure describes a polycarbonate blend composition
  • a polycarbonate blend composition comprising: (a) a polycarbonate homopolymer; (b) a first polysiloxane-polycarbonate copolymer comprising: (i) poly diorganosiloxane blocks comprising repeating structural units of formula:
  • polydiorganosiloxane block length (E) is from 30 to 60; and (ii) polycarbonate blocks comprising polycarbonate units of formula: wherein at least 60 percent of the total number of R 1 groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the first polysiloxane -polycarbonate copolymer comprises a diorganosiloxane content of from 4 to 8 wt % diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer; (c) a second polysiloxane-polycarbonate copolymer comprising: (i) polydiorganosiloxane blocks comprising repeating structural units of formula:
  • polydiorganosiloxane block length (E) is from 30 to 100; and (ii) polycarbonate blocks comprising polycarbonate units of formula:
  • R— O C O wherein at least 60 percent of the total number of R 1 groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the second polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 15 to 30 wt % diorganosiloxane based on the total weight of the second
  • the blend composition has an average melt flow rate (MFR) of 7 or greater measured at 300 °C/1.2 kg; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has a black color characterized by an average L* value of 27 or less as measured by the CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -30 °C of 650 J/m or greater and a % ductility of 100% according to ASTM D256-2010.
  • MFR average melt flow rate
  • the invention relates to polycarbonate blend compositions comprising: (a) a first polysiloxane-polycarbonate copolymer comprising: i)
  • polydiorganosiloxane blocks comprising repeating structural units of formula:
  • polydiorganosiloxane block length (E) is from 30 to 60; and ii) polycarbonate blocks comprising polycarbonate units of formula:
  • the first polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 4 to 8 wt % diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer; (b) a second polysiloxane-polycarbonate copolymer comprising: i)
  • polydiorganosiloxane blocks comprising repeating structural units of formula:
  • polydiorganosiloxane block length (E) is from 30 to 100; and ii) polycarbonate blocks comprising polycarbonate units of formula:
  • the second polysiloxane -polycarbonate copolymer comprises a diorganosiloxane content of from 15 to 30 wt % diorganosiloxane based on the total weight of the second
  • the blend composition has an average melt flow rate (MFR) of 7 or greater measured at 300 °C/1.2 kg; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has a black color characterized by an average L* value of 28 or less as measured by the CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -30 °C of 600 J/m or greater and a % ductility of 80% according to ASTM D256-2010; and wherein R is the same or different, and is a C 1-13 monovalent organic group; R 2 is independently a divalent C1-C30 organic group; M is independently a halogen, cyano, nitro, Ci-C 8 alkyl
  • the invention relates to polycarbonate blend compositions comprising: (a) a polycarbonate polymer; (b) a first polysiloxane-polycarbonate copolymer comprising: i) polydiorganosiloxane blocks comprising repeating structural units of formula:
  • polydiorganosiloxane block length (E) is from 30 to 60; and ii) polycarbonate blocks comprising polycarbonate units of formula:
  • the first polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 4 to 8 wt % diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer; (c) a second polysiloxane-polycarbonate copolymer comprising: i)
  • polydiorganosiloxane blocks comprising repeating structural units of formula:
  • polydiorganosiloxane block length (E) is from 30 to 100; and ii) polycarbonate blocks comprising polycarbonate units of formula:
  • the second polysiloxane -polycarbonate copolymer comprises a diorganosiloxane content of from 15 to 30 wt % diorganosiloxane based on the total weight of the second
  • the blend composition has an average melt flow rate (MFR) of 7 or greater measured at 300°C/1.2 kg; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has a black color characterized by an average L* value of 28 or less as measured by the CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -30°C of 600 J/m or greater and a % ductility of 80% according to ASTM D256-2010; and wherein R is the same or different, and is a C 1-13 monovalent organic group; R 2 is independently a divalent C 1 -C 30 organic group; M is independently a halogen, cyano, nitro, Ci-C 8 alkylthi
  • each R 2 is independently a divalent C 1 -C 30 organic group such as a C 1 -C30 alkyl, C 6 -C 30 aryl or C 7 -C30 alkylaryl.
  • Each M in the polydiorganosiloxane can be the same or different, and is a halogen, cyano, nitro, Ci-Cs alkylthio, Ci-Cg alkyl, Ci-Cg alkoxy, C2-C8 alkenyl, C2-C8 alkenyloxy group, C3-C8 cycloalkyl, C3-C8 cycloalkoxy, C 6 -Cio aryl, C 6 -Cio aryloxy, C7-C12 aralkyl, C 7 - C 12 aralkoxy, C 7 - C 12 alkylaryl, or C 7 - C 12 alkylaryloxy, wherein each n is independently 0, 1, 2, 3, or 4.
  • R 2 is a dimethylene, trimethylene or tetramethylene group; and
  • R is a CI -8 alkyl, haloalkyl such as trifluoropropyl, cyanoalkyl, or aryl such as phenyl, chlorophenyl or tolyl.
  • R is methyl, or a combination of methyl and trifluoropropyl, or a combination of methyl and phenyl.
  • M is methoxy
  • n is one
  • R 2 is a divalent C1-C3 aliphatic group
  • R is methyl.
  • the polycarbonate polymer may be derived from one dihydroxy monomer or a combination of two or more dihydroxy aromatic monomers, respectively.
  • polycarbonate and polycarbonate resin means compositions having repeating structural carbonate units of the formula (I):
  • each R 1 is an aromatic organic group, for example a group of the formula (II):
  • each of A 1 and A 2 is a monocyclic divalent aryl group and Y 1 is a bridging group having one or two atoms that separate A 1 from A 2 .
  • one atom may separate A 1 from A 2 , with illustrative examples of these groups including -0-, -S-, -S(O)-, -S(0) 2 -, -C(O)-, methylene, cyclohexyl-methylene, 2-[2.2.1]-bicycloheptylidene, ethylidene, isopropylidene, neopentylidene, cyclohexylidene, cyclopentadecylidene, cyclododecylidene, and
  • the bridging group Y 1 may be a hydrocarbon group or a saturated hydrocarbon group such as methylene, cyclohexylidene, or isopropylidene.
  • the polycarbonates may be produced from dihydroxy compounds having the formula HO-R ⁇ OH, wherein R 1 is defined as above for formula (I).
  • R 1 is defined as above for formula (I).
  • HO-R ⁇ OH includes bisphenol compounds of formula (III):
  • R a and R b each represent a halogen atom or a monovalent hydrocarbon group and may be the same or different; p and q are each independently integers of 0 to 4; and X a represents one of the groups of formula (V):
  • R c and R d each independently represent a hydrogen atom or a monovalent linear alkyl or cyclic alkylene group and R e is a divalent hydrocarbon group.
  • R c and R d represent a cyclic alkylene group; or a heteroatom-containing cyclic alkylene group comprising carbon atoms and heteroatoms with a valency of two or greater.
  • a heteroatom-containing cyclic alkylene group comprises at least one heteroatom with a valency of 2 or greater, and at least two carbon atoms.
  • Suitable heteroatoms for use in the heteroatom-containing cyclic alkylene group include -0-, -S-, and -N(Z)-, where Z is a substituent group selected from hydrogen, Ci_i 2 alkyl, Ci_i 2 alkoxy, or Ci_i 2 acyl.
  • the cyclic alkylene group or heteroatom-containing cyclic alkylene group may have 3 to 20 atoms, and may be a single saturated or unsaturated ring, or fused polycyclic ring system wherein the fused rings are saturated, unsaturated, or aromatic.
  • each R h is independently a halogen atom, a Cno hydrocarbyl such as a Ci_io alkyl group, a halogen substituted Ci_io hydrocarbyl such as a halogen-substituted Ci_io alkyl group, and n is 0 to 4.
  • the halogen is usually bromine, though it is not limited to only bromine.
  • Some exemplary dihydroxy compounds include: 4,4'-dihydroxybiphenyl, 1 ,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)- 1 -naphthylmethane,
  • resorcinol 3,6-dihydroxydibenzothiophene, and 2,7-dihydroxycarbazole, resorcinol, substituted resorcinol compounds such as 5 -methyl resorcinol, 5 -ethyl resorcinol, 5 -propyl resorcinol, 5 -butyl resorcinol, 5-t-butyl resorcinol, 5 -phenyl resorcinol, 5-cumyl resorcinol,
  • hydroquinone substituted hydroquinones such as 2-methyl hydroquinone, 2-ethyl
  • hydroquinone 2-propyl hydroquinone, 2-butyl hydroquinone, 2-t-butyl hydroquinone, 2-phenyl hydroquinone, 2-cumyl hydroquinone, 2,3,5,6-tetramethyl hydroquinone,
  • bisphenol compounds that may be represented by formula (3) include l,l-bis(4-hydroxyphenyl) methane, l,l-bis(4-hydroxyphenyl) ethane,
  • bisphenol A 2,2-bis(4-hydroxyphenyl) propane
  • DMBPC 1 , 1 -bis(4-hydroxy-3 -methylphenyl)cyclohexane
  • polycarbonates with branching groups can be useful, provided that such branching does not significantly adversely affect desired properties of the polycarbonate.
  • Branched polycarbonate blocks can be prepared by adding a branching agent during polymerization.
  • branching agents include poly functional organic compounds containing at least three functional groups selected from hydroxyl, carboxyl, carboxylic anhydride, haloformyl, and mixtures of the foregoing functional groups.
  • trimellitic acid trimellitic anhydride, trimellitic trichloride, tris-p-hydroxy phenyl ethane, isatin-bis-phenol, tris-phenol TC (l,3,5-tris((p-hydroxyphenyl)isopropyl)benzene), tris-phenol PA (4-(4'-(l,l-bis(p-hydroxyphenyl)-ethyl) alpha, alpha-dimethylbenzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid, and benzophenone tetracarboxylic acid.
  • a branching agent can be added at a level of about 0.05 to about 2.0 wt %.
  • mixtures comprising linear polycarbonates and branched polycarbonates can be used.
  • the composition may include, as the polycarbonate polymer, at least one bisphenol-A polycarbonate polymer.
  • the polycarbonate polymer at least one bisphenol-A polycarbonate polymer.
  • polycarbonate may include high and low flow LexanTM polycarbonate polymers available in various grades from SABIC Innovative Plastics.
  • the polycarbonate may be present in the composition as a total amount ranging from 5 wt % to 60 wt %. In another aspect, the polycarbonate may be present in the composition as a total amount ranging from 10 wt % to 55 wt %. In a further aspect, the polycarbonate may be present in the composition as a total amount ranging from 10 wt % to 50 wt %. In an even further aspect, the polycarbonate may be present in the composition as a total amount ranging from 15 wt% to 45 wt %. The polycarbonate may be present as a single bisphenol-A polycarbonate or as a mixture of two or more bisphenol-A polycarbonates.
  • one polycarbonate may be present in the composition in an amount ranging from 1 wt % to 60 wt %. In a further aspect, one polycarbonate may be present in an amount ranging from 3 wt % to 55 wt %. In another aspect, one polycarbonate may be present in an amount ranging from 3 wt % to 50 wt %. In a still further aspect, one polycarbonate may be present in an amount ranging from 5 wt % to 45 wt %. In a yet further aspect, the polycarbonate polymer is present in an amount in the range of from 15 wt% to 30 wt% relative to the total weight percent of the polycarbonate polymer, first
  • polysiloxane -polycarbonate copolymer and second polysiloxane-polycarbonate copolymer.
  • the polycarbonate polymer is present in an amount in the range of from 22 wt% to 29 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
  • the polycarbonate polymer is present in an amount in the range of from 15 wt% to 45 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer. In a still further aspect, the polycarbonate polymer is present in an amount in the range of from 24 wt% to 45 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second
  • polysiloxane-polycarbonate copolymer is present in an amount in the range of from 0 wt% to 55 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer. In an even further aspect, the polycarbonate polymer is present in an amount in the range of from 0 wt% to 45 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
  • the bisphenol-A polycarbonate has a weight-averaged molecular weight, Mw, between 18,000 and 32,000 g/mol.
  • Mw weight-averaged molecular weight
  • Bisphenol-A polycarbonate has a weight-averaged molecular weight, Mw, between 28,000 and 32,000 g/mol.
  • Mw weight-averaged molecular weight
  • the weight-average molecular weight may be measured using GPC.
  • the weight-average molecular weight may be measured using standard procedures, for example, using the method of ASTM D1003.
  • the polycarbonate polymer comprises a first polycarbonate polymer and a second polycarbonate polymer.
  • the first polycarbonate polymer is a low flow polycarbonate.
  • the second polycarbonate polymer is a high flow polycarbonate.
  • the first polycarbonate polymer is present in an amount in the range of from 11 wt% to 29 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second
  • the second polycarbonate polymer is present in an amount in the range of from greater than 0 wt% to 8 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
  • the first polycarbonate polymer is present in an amount in the range of from 14 wt% to 29 wt% relative to the total weight percent of the polycarbonate polymer, first
  • polysiloxane-polycarbonate copolymer and second polysiloxane-polycarbonate copolymer and wherein the second polycarbonate polymer is present in an amount in the range of from greater than 0 wt% to 8 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane -polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
  • the first polycarbonate polymer is present in an amount in the range of from 10 wt% to 30 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second
  • polysiloxane-polycarbonate copolymer and wherein the second polycarbonate polymer is present in an amount in the range of from greater than 0 wt% to 15 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
  • the polysiloxane-polycarbonate copolymer has a polysiloxane structural unit and a polycarbonate structural unit.
  • polysiloxane-polycarbonate copolymer may be derived from carbonate units of formula (I) as described above.
  • the carbonate units may be derived from one or more dihydroxy monomers of formula (III) including bisphenol compound of formula (IV), both as described and incorporated herein from above.
  • the dihydroxy compound may be bisphenol-A.
  • R is the same or different, and is a Ci_i 3 monovalent organic group.
  • R can be a C 1 -C 13 alkyl group, Ci- C 13 alkoxy group, C 2 - C 13 alkenyl group, C 2 - Ci 3 alkenyloxy group, C 3 -C 6 cycloalkyl group, C 3 -C 6 cycloalkoxy group, C 6 -Ci 4 aryl group, C 6 -Cio aryloxy group, C 7 - C 13 aralkyl group, C 7 - C 13 aralkoxy group, C 7 - C 13 alkylaryl group, or C 7 - Ci 3 alkylaryloxy group.
  • the foregoing groups can be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof.
  • R does not contain any halogen. Combinations of the foregoing R groups can be used in the same polymer.
  • the polysiloxane structural unit may be derived from a siloxane-containing dihydroxy compounds (also referred to herein as "hydroxyaryl end-capped polysiloxanes”) that contain diorganosiloxane unit blocks of formula (IX):
  • R can be a C 1 -C 13 alkyl group, Ci- C 13 alkoxy group, C 2 - C 13 alkenyl group, C 2 - Ci3 alkenyloxy group, C3-C6 cycloalkyl group, C3-C6 cycloalkoxy group, C 6 -Ci4 aryl group, C 6 -Cio aryloxy group, C 7 - C 13 aralkyl group, C 7 - C 13 aralkoxy group, C 7 - C 13 alkylaryl group, or C 7 - Ci3 alkylaryloxy group.
  • the foregoing groups can be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof.
  • R does not contain any halogen. Combinations of the foregoing R groups can be used in the same polycarbonate.
  • E in formula (IX) can vary widely depending on the type and relative amount of each of the different units in the polycarbonate, the desired properties of the polycarbonate, and like considerations.
  • E can have an average value of about 2 to about 1 ,000, specifically about 2 to about 500, more specifically about 2 to about 100.
  • E has an average value of about 4 to about 90, specifically about 5 to about 80, and more specifically about 40 to about 60.
  • polysiloxane blocks are provided by repeating structural units of formula (X):
  • E is as defined above; each R is the same or different, and is as defined above; and each Ar is the same or different, and Ar is one or more C6-C30 aromatic group(s), or one or more alkyl containing C6-C30 aromatic group(s), wherein the bonds are directly connected to an aromatic moiety.
  • the — O— Ar— O— groups in formula (X) can be, for example, a C6-C30 dihydroxyaromatic compound. Combinations comprising at least one of the foregoing dihydroxyaromatic compounds can also be used. Exemplary dihydroxyaromatic compounds are l ,l-bis(4-hydroxyphenyl) methane, l ,l-bis(4-hydroxyphenyl)ethane,
  • omega-bis-acetoxy-polydiorganosiloxane oligomer under phase transfer conditions.
  • polydiorganosiloxane blocks can comprise units of formula (XII):
  • each 5 is independently a divalent C 1 -C30 organic group such as a C1-C30 alkyl, C6-C30 aryl or C7-C30 alkylaryl.
  • the polysiloxane blocks corresponding to formula (XII) are derived from the corresponding dihydroxy compound of formula (XIII):
  • polydiorganosiloxane blocks are provided by repeating structural units of formula (XIV):
  • R 7 in formula (XIV) is a divalent C2-C8 aliphatic group.
  • Each M in formula (XIV) can be the same or different, and is a halogen, cyano, nitro, Ci-Cg alkylthio, Ci-Cg alkyl, Ci-Cg alkoxy, C 2 -Cg alkenyl, C 2 -Cg alkenyloxy group, C 3 -Cg cycloalkyl, C 3 -Cg cycloalkoxy, C 6 -Cio aryl, C 6 -Cio aryloxy, C 7 -Ci 2 aralkyl, C 7 - Ci 2 aralkoxy, C 7 - C12 alkylaryl, or C 7 - C 12 alkylaryloxy, wherein each n is independently 0, 1, 2, 3, or 4.
  • R 7 is a dimethylene, trimethylene or tetramethylene group; and
  • R is a Ci_g alkyl, haloalkyl such as trifluoropropyl, cyanoalkyl, or aryl such as phenyl, chlorophenyl or tolyl.
  • R is methyl, or a combination of methyl and trifluoropropyl, or a combination of methyl and phenyl.
  • M is methoxy
  • n is one
  • R 7 is a divalent Ci-C 3 aliphatic group
  • R is methyl.
  • Polysiloxane-polycarbonates comprising units of formula (XIV) can be derived from the corresponding dihydroxy polydiorganosiloxane of formula (XV):
  • R and E are as previously defined, and an aliphatically unsaturated monohydric phenol.
  • exemplary aliphatically unsaturated monohydric phenols included, for example, eugenol, 2-allylphenol, 4-allyl-2-methylphenol, 4-allyl-2-phenylphenol,
  • the polysiloxane polycarbonate copolymer can be a block copolymer of polycarbonate and eugenol capped polydimethylsilioxane (PDMS) having the general structure (XVII) as shown below:
  • polysiloxane -polycarbonate block copolymer comprises polycarbonate blocks derived from Bisphenol-A and diorganopolysiloxane blocks of the general formula (XVIII):
  • the polysiloxane block length "X" of formula (XVIII) is from about 40 to about 60.
  • the polysiloxane-polycarbonate block copolymer can optionally be end-capped with p-cumyl-phenol.
  • Diorganopolysiloxane blocks of formula (XVIII) can be derived from the corresponding dihydroxy compound of formula (XIX):
  • the polycarbonate -polysiloxane copolymer may be manufactured by reaction of a dihydroxy polysiloxane with a carbonate source and a dihydroxy aromatic compound such as bisphenol-A, optionally in the presence of a phase transfer catalyst as described above.
  • Suitable conditions are similar to those useful in forming polycarbonates as described above.
  • the copolymers are prepared by phosgenation, at temperatures from below 0 °C to about 100 °C, preferably about 25 °C to about 50 °C. Since the reaction is exothermic, the rate of phosgene addition may be used to control the reaction temperature. The amount of phosgene required will generally depend upon the amount of the dihydric reactants.
  • the polycarbonate-polysiloxane copolymers may be prepared by co-reacting in a molten state, the dihydroxy monomers and a diaryl carbonate ester, such as diphenyl carbonate, in the presence of a transesterification catalyst as described above.
  • the amount of dihydroxy diorganopolysiloxane is selected so as to provide the desired amount of
  • diorganopolysiloxane units in the copolymer in the copolymer.
  • the particular amounts used will therefore be determined depending on desired physical properties of the composition, the value of x (within the range of about 40 to about 60), and the type and relative amount of each component in the composition, including the type and amount of polycarbonate, type and amount of impact modifier, type and amount of polycarbonate-polysiloxane copolymer, and type and amount of any other additives.
  • diorganopolysiloxane can be determined by one of ordinary skill in the art without undue experimentation using the guidelines taught herein.
  • the amount of dihydroxy polydiorganosiloxane may be selected so as to produce a copolymer comprising about 20 wt.% polydimethylsiloxane.
  • the copolymer may comprise about 20 wt.% siloxane.
  • the polysiloxane units are of formula (9)
  • each R is independently a Ci_i3 monovalent hydrocarbyl group.
  • each R can independently be a Ci_i 3 alkyl group, Ci_i 3 alkoxy group, C 2-13 alkenyl group, C 2-13 alkenyloxy group, C 3 _ 6 cycloalkyl group, C 3 _ 6 cycloalkoxy group, C 6-14 aryl group, C 6 -io aryloxy group, C 7-13 arylalkyl group, C 7-13 arylalkoxy group, C 7-13 alkylaryl group, or C 7-13 alkylaryloxy group.
  • the foregoing groups can be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof.
  • the polysiloxane comprises R groups that have minimal hydrocarbon content.
  • an R group with a minimal hydrocarbon content is a methyl group.
  • the average value of E in formula (9) can vary widely depending on the type and relative amount of each component in the thermoplastic composition, whether the polymer is linear, branched or a graft copolymer, the desired properties of the composition, and like considerations.
  • E has an average value of 2 to 500, 2 to 200, or 5 to 100, 10 to 100, or 10 to 80.
  • E has an average value of 16 to 50, more specifically 20 to 45, and even more specifically 25 to 45.
  • E has an average value of 4 to 50, 4 to 15, specifically 5 to 15, more specifically 6 to 15, and still more specifically 7 to 10.
  • the pol siloxane units are structural units of formula (9a)
  • each R can independently be the same or different, and is as defined above; and each Ar can independently be the same or different, and is a substituted or unsubstituted C 6 -3o compound containing an aromatic group, wherein the bonds are directly connected to the aromatic moiety.
  • the Ar groups in formula (9a) can be derived from a C 6 _3o dihydroxy aromatic compound, for example a bisphenol compound as described above or a monoaryl dihydroxy compound (6) above. Combinations comprising at least one of the foregoing dihydroxy aromatic compounds can also be used.
  • dihydroxy aromatic compounds are resorcinol (i.e., 1,3-dihydroxybenzene), 4-methyl-l,3-dihydroxybenzene, 5-methyl- 1 ,3-dihydroxybenzene, 4,6-dimethyl- 1 ,3-dihydroxybenzene, 1 ,4-dihydroxybenzene,
  • the dihydroxy aromatic compound is unsubstituted, or is does not contain non-aromatic hydrocarbyl substituents such as alkyl, alkoxy, or alkylene substituents.
  • the polysiloxane units are of the formula(9a-l)
  • the first polysiloxance-polycarbonate has an average haze of less than 2.5 %.
  • the first polysiloxane-polycarbonate, the polydiorganosiloxane block length (E) is from 30 to 60. In one aspect, E is from 40 to 60, from 30 to 50, from 50 to 60, from 40 to 50, or from 30 to 40.
  • each R 2 is independently a divalent Ci-C 30 organic group such as a Ci-C 3 o alkyl, C 6 -C 3 o aryl or C 7 -C 3 o alkylaryl.
  • the first polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 4 to 8 wt % diorganosiloxane based on the total weight of the first
  • the first polysiloxane-polycarbonate copolymer may comprise a diorganosiloxane content of from 4 to 7 wt %, or from 5 to 7 wt% diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer.
  • the first polysiloxane-polycarbonate copolymer may comprise a
  • diorganosiloxane content of about 6 wt % diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer.
  • the second polysiloxane-polycarbonate the polydiorganosiloxane block length (E) is from 30 to 100. In one aspect, E is from 40 to 90, from 50 to 80, from 60 to 70, from 30 to 50, from 50 to 100, or from 50 to 70.
  • the second polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 15 to 30 wt % diorganosiloxane based on the total weight of the second polysiloxane-polycarbonate copolymer.
  • the second diorganosiloxane content of from 15 to 30 wt % diorganosiloxane based on the total weight of the second polysiloxane-polycarbonate copolymer.
  • polysiloxane-polycarbonate copolymer may comprise a diorganosiloxane content of from 15 to 25 wt %, from 17 to 23 wt %, or from 19 to 21 wt % diorganosiloxane based on the total weight of the second polysiloxane-polycarbonate copolymer.
  • the second polysiloxane-polycarbonate copolymer may comprise a diorganosiloxane content of about 20 wt % diorganosiloxane based on the total weight of the second polysiloxane-polycarbonate copolymer
  • the first polysiloxane-polycarbonate copolymer has an weight-averaged molecular weight, Mw, between 20,000 and 25,000 g/mol and injection molded parts from the blend composition have an average haze of less than 2.5 % at a thickness of 3.2 mm, using the method of ASTM D1003.
  • the weight-averaged molecular weight, Mw ranges from 21,000 to 24,000 g/mol, for example ranging from 22,000 to 24,000 g/mol.
  • the weight-average molecular weight may be measured using Gel Permeation Chromatography (GPC) using polycarbonate standards.
  • molecular weight determinations can be performed using gel permeation chromatography (GPC), using a crosslinked styrene-divinylbenzene column and calibrated to polycarbonate references.
  • GPC gel permeation chromatography
  • samples are prepared at a concentration of about 1 mg/ml, and are eluted at a flow rate of about 1.0 ml/min.
  • the first polysiloxane-polycarbonate copolymer has an weight-averaged molecular weight, Mw, in the range of from 20,000 to 25,000 and wherein an injection molded part having a thickness of 3.2 mm formed from the blend composition has an average haze of less than 2.5 % measured according to ASTM D1003.
  • the first polysiloxane-polycarbonate copolymer has a
  • PolyDispersitylndex ranging from 2 to 5, for example ranging from 2 to 4, or from 2 to
  • the second polysiloxane-polycarbonate copolymer has a
  • PolyDispersitylndex ranging from 2 to 5, for example ranging from 2 to 4, or from 2 to ">
  • the second polysiloxane-polycarbonate copolymer has a weight-averaged molecular weight, Mw, between 25,000 and 35,000 g/mol.
  • Mw weight-averaged molecular weight
  • the weight-averaged molecular weight, Mw ranges from 27,000 to 33,000 g/mol, for example, ranging from 28,000 to 32,000 g/mol, further for example, 29,000 to 31,000 g/mol.
  • the weight-average molecular weight may be measured using Gel Permeation Chromatography (GPC) using polycarbonate standards.
  • the weight-average molecular weight may be measured using standard procedures, for example, using the method of ASTM D1003.
  • composition may comprise at least one
  • polysiloxane-polycarbonate copolymers which may be used include a transparent polysiloxane-polycarbonate copolymer with a Mw of 23,000 g/mol, 6.0% siloxane, percent haze less than 2.5, or an opaque polysiloxane-polycarbonate copolymer with a Mw of 30,000 g/mol, 20.0% siloxane.
  • the second polysiloxane-polycarbonate copolymer is an opaque resin.
  • polysiloxane-polycarbonate copolymer are dimethyl siloxane units.
  • the polydiorganosiloxane has moieties derived from eugenol, 4-allylphenol, or 2-allylphenol
  • the composition may comprise a total amount of polycarbonate copolymer ranging from 50 wt % to 95 wt %. In another aspect, the composition may comprise a total amount of polycarbonate copolymer ranging from 60 wt % to 90 wt %. In a further aspect, the composition may comprise a total amount of polysiloxane-polycarbonate copolymer ranging from 65 wt % to 90 wt %. In one aspect, the composition may comprise a total amount of polysiloxane-polycarbonate copolymer ranging from 70 wt % to 85 wt %. The polysiloxane-polycarbonate copolymer may be present as a single
  • polysiloxane-polycarbonate or as a mixture of two or more polysiloxane -polycarbonates.
  • At least one polysiloxane-polycarbonate copolymer may be present in an amount ranging from 1 wt % to 95 wt%. In a further aspect, at least one
  • polysiloxane-polycarbonate copolymer may be present in an amount ranging from 2 wt % to 90 wt %. In another aspect, at least one polysiloxane-polycarbonate copolymer may be present in an amount ranging from 2 wt % to 85 wt %. In one aspect, the second polysiloxane-polycarbonate copolymer has at least 5 wt %. In another aspect, the second polysiloxane-polycarbonate copolymer ranges from 5 wt % to 95 wt %.
  • the second polysiloxane-polycarbonate copolymer is present in the blend composition in an amount less than 5 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second
  • the second polysiloxane-polycarbonate copolymer is present in the blend composition in an amount of about 2.5 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second
  • polysiloxane-polycarbonate copolymer is present in the blend composition in an amount of about 4 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
  • the second polysiloxane-polycarbonate copolymer is present in the blend composition in an amount less than 5 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second
  • the total weight percentage of siloxane ranges from 4.5 wt % to 5.5 wt % based on the total combined weight of the first polysiloxane-polycarbonate, second polysiloxane-polycarbonate, and polycarbonate.
  • the total weight percentage of siloxane ranges from 4.5 wt % to 5.3 wt % based on the total combined weight of the first polysiloxane-polycarbonate, second polysiloxane-polycarbonate, and polycarbonate.
  • the total weight percentage of siloxane ranges from 4.5 wt % to 5.0 wt % based on the total combined weight of the first polysiloxane-polycarbonate, second
  • the total weight percentage of siloxane ranges from 4.6 wt % to 4.9 wt % based on the total combined weight of the first polysiloxane-polycarbonate, second polysiloxane-polycarbonate, and
  • the total weight percentage of siloxane is 4.98 wt % based on the total combined weight of the first polysiloxane-polycarbonate, second
  • polysiloxane-polycarbonate and polycarbonate.
  • the total weight percentage of siloxane ranges from 4.0 wt % to 6.6 wt % based on the total combined weight of the first polysiloxane-polycarbonate, second polysiloxane-polycarbonate, and the polycarbonate. In a still further aspect, the total weight percentage of siloxane ranges from 4.0 wt % to 7 wt % based on the total combined weight of the first polysiloxane-polycarbonate, second polysiloxane-polycarbonate, and the polycarbonate.
  • the total combined weight percent of the first and second polysiloxane-polycarbonate copolymers present in the blend composition is in the range of from 70 wt% to 80 wt% relative to the total combined weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second
  • the total combined weight percent of the first and second polysiloxane-polycarbonate copolymers present in the blend composition is in the range of from 54 wt% to 100 wt% relative to the total combined weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
  • the first polysiloxane-polycarbonate copolymer is present in an amount in the range of from 50 wt% to 95 wt% relative to the total combined weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
  • the first polysiloxane-polycarbonate copolymer is present in an amount in the range of from 65 wt% to 75 wt% relative to the total combined weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
  • the second polysiloxane -polycarbonate copolymer is present in an amount in the range of from greater than 0 wt% to 5 wt% relative to the total combined weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second
  • the total combined weight percent of the first and second polysiloxane-polycarbonate copolymers present in the blend composition is in the range of from 50 wt% to 90 wt% relative to the total combined weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second
  • the first polysiloxane-polycarbonate copolymer is present in an amount in the range of from 50 wt% to 85 wt% relative to the total combined weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
  • the second polysiloxane-polycarbonate copolymer is present in an amount in the range of from 50 wt% to 85 wt% relative to the total combined weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
  • the second polysiloxane-polycarbonate copolymer is present in an amount in the range of from 50 wt% to 85 wt% relative to the total combined weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polys
  • polysiloxane-polycarbonate copolymer is present in an amount in the range of from greater than 0 wt% to 5 wt% relative to the total combined weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second
  • the disclosed composition comprises a colorant composition.
  • the colorant composition comprises primarily organic colorants. As such, the composition comprises less than 1.5 wt % of an inorganic colorant based on the total colorant composition. In another aspect, the composition comprises an inorganic colorant based on the total weight of the composition ranging from 0.25 wt % to 1.5 wt %. In one aspect, the inorganic colorant is carbon black. As such, the composition comprises carbon black in an amount less than 1.5 wt % of the total colorant composition.
  • the colorant composition comprises less than 12 wt % of an inorganic colorant based on the total weight of the colorant composition. In a still further aspect, the colorant composition comprises less than 10 wt % of an inorganic colorant based on the total weight of the colorant composition. In a yet further aspect, the colorant composition comprises less than 8 wt % of an inorganic colorant based on the total weight of the colorant composition. In an even further aspect, the colorant composition comprises less than 6 wt % of an inorganic colorant based on the total weight of the colorant composition. In a still further aspect, the colorant composition comprises less than 5 wt % of an inorganic colorant based on the total weight of the colorant composition. OPTIONAL POLYMER ADDITIVES
  • the disclosed polycarbonate blend compositions can optionally comprise a balance amount of one or more additive materials ordinarily incorporated in polycarbonate resin compositions of this type, with the proviso that the additives are selected so as to not significantly adversely affect the desired properties of the polycarbonate composition.
  • Combinations of additives can be used. Such additives can be mixed at a suitable time during the mixing of the components for forming the composition.
  • additive materials that can be present in the disclosed polycarbonate compositions include an acid scavenger, anti-drip agent, antioxidant, antistatic agent, chain extender, colorant (e.g., pigment and/or dye), de-molding agent, flow promoter, lubricant, mold release agent, plasticizer, quenching agent, stabilizer (including for example a thermal stabilizer, a hydrolytic stabilizer, or a light stabilizer), UV absorbing additive, and UV reflecting additive, or any combination thereof.
  • colorant e.g., pigment and/or dye
  • de-molding agent e.g., flow promoter, lubricant, mold release agent, plasticizer, quenching agent, stabilizer (including for example a thermal stabilizer, a hydrolytic stabilizer, or a light stabilizer), UV absorbing additive, and UV reflecting additive, or any combination thereof.
  • the disclosed composition can comprise one or more fillers, acids, specialty chemicals stabilizers, flame-retardants, impact modifiers, colorant, and/or mold release agents.
  • the disclosed composition can comprise Irgaphos 168 Ciba Specialty Chemicals and pigments.
  • the disclosed composition may also comprise dilute phosphorous acid, for example 100 times dilution.
  • the disclosed polycarbonate blend compositions can further comprise a primary antioxidant or "stabilizer” (e.g., a hindered phenol) and, optionally, a secondary antioxidant (e.g., a phosphate and/or thioester).
  • a primary antioxidant or "stabilizer” e.g., a hindered phenol
  • a secondary antioxidant e.g., a phosphate and/or thioester
  • Suitable antioxidant additives include, for example, organic phosphites such as tris(nonyl phenyl)phosphite,
  • alkylated reaction products of polyphenols with dienes such as
  • butylated reaction products of para-cresol or dicyclopentadiene alkylated hydroquinones; hydroxylated thiodiphenyl ethers; alkylidene-bisphenols; benzyl compounds; esters of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid with monohydric or polyhydric alcohols; esters of beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydric or polyhydric alcohols; esters of thioalkyl or thioaryl compounds such as distearylthiopropionate, dilaurylthiopropionate, ditridecylthiodipropionate,
  • the antioxidant is a primary antioxidant, a secondary antioxidant, or combinations thereof.
  • the primary antioxidant is selected from a hindered phenol and secondary aryl amine, or a combination thereof.
  • the hindered phenol comprises one or more compounds selected from triethylene glycol bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],
  • the hindered phenol comprises octadecyl-3 -(3 ,5 -di-t-butyl-4-hydroxyphenyl)-propionate .
  • the secondary anti-oxidant is selected from an
  • the secondary anti-oxidant comprises one or more compounds selected from
  • the secondary anti-oxidant comprises tris(2,4-di-tert-butylphenyl) phosphite.
  • Antioxidants are generally used in amounts of about 0.01 wt% to about 3 wt%, optionally about 0.05 wt% to about 2.0 wt% of the blended thermoplastic composition.
  • the primary antioxidant is present in an amount from about 0.01 wt% to about 3 wt%. In another aspect, the primary antioxidant is present in an amount from about 0.01 wt% to about 2.5 wt%. In still another aspect, the primary antioxidant is present in an amount from about 0.5 wt% to about 2.5 wt%. In yet a further aspect, the primary antioxidant is present in an amount from about 0.5 wt% to about 2.0 wt%. In still another aspect, the primary antioxidant is present in an amount from about 0.1 wt% to about 0.5 wt%. In still another aspect, the primary antioxidant is present in an amount from about 0.2 wt% to about 0.5 wt%. In still another aspect, the primary antioxidant is present in an amount from about 0.2 wt% to about 0.4 wt%.
  • the secondary antioxidant is present in an amount from about 0.01 wt% to about 3.0 wt%. In another aspect, the secondary antioxidant is present in an amount from about 0.01 wt% to about 2.5 wt%. In still another aspect, the secondary antioxidant is present in an amount from about 0.5 wt% to about 2.5 wt%. In yet another aspect, the secondary antioxidant is present in an amount from about 0.5 wt% to about 2.0 wt%. In still another aspect, the secondary antioxidant is present in an amount from about 0.05 wt% to about 0.4 wt%. In still another aspect, the secondary antioxidant is present in an amount from about 0.05 wt% to about 0.2 wt%.
  • the disclosed polycarbonate blend compositions further comprise a hydrolytic stabilizer, wherein the hydrolytic stabilizer comprises a hydrotalcite and an inorganic buffer salt.
  • the disclosed polycarbonate blend composition comprises a hydrolytic stabilizer, wherein the hydrolytic stabilizer comprises one or more hydrotalcites and an inorganic buffer salt comprising one or more inorganic salts capable of pH buffering. Either synthetic hydrotalcites or natural hydrotalcites can be used as the hydrotalcite compound in the present invention.
  • Exemplary hydrotalcites that are useful in the compositions of the present are commercially available and include, but are not limited to, magnesium hydrotalcites such as DHT-4C (available from Kyowa Chemical Co.); Hysafe 539 and Hysafe 530 (available from J.M. Huber Corporation).
  • magnesium hydrotalcites such as DHT-4C (available from Kyowa Chemical Co.); Hysafe 539 and Hysafe 530 (available from J.M. Huber Corporation).
  • suitable thermal stabilizer additives include, for example, organic phosphites such as triphenyl phosphite, tris-(2,6-dimethylphenyl)phosphite, tris-(mixed mono-and di-nonylphenyl)phosphite or the like; phosphonates such as dimethylbenzene phosphonate or the like, organic phosphates such as trimethyl phosphate, thioesters such as pentaerythritol betalaurylthiopropionate, and the like, or combinations comprising at least one of the foregoing thermal stabilizers.
  • organic phosphites such as triphenyl phosphite, tris-(2,6-dimethylphenyl)phosphite, tris-(mixed mono-and di-nonylphenyl)phosphite or the like
  • phosphonates such as dimethylbenzene phosphonate or the like
  • organic phosphates
  • Thermal stabilizers are generally used in amounts of about 0.01 wt% to about 5 wt%, optionally about 0.05 wt% to about 2.0 wt% of the polycarbonate blend composition. In one aspect, the thermal stabilizer is present in an amount from about 0.01 wt% to about 3.0 wt%. In another aspect, the thermal stabilizer is present in an amount from about 0.01 wt% to about 2.5 wt%. In still another aspect, the thermal stabilizer is present in an amount from about 0.5 wt% to about 2.5 wt%. In still another aspect, the thermal stabilizer is present in an amount from about 0.5 wt% to about 2.0 wt%.
  • the thermal stabilizer is present in an amount from about 0.1 wt% to about 0.8 wt%. In still another aspect, the thermal stabilizer is present in an amount from about 0.1 wt% to about 0.7 wt%. In still another aspect, the thermal stabilizer is present in an amount from about 0.1 wt% to about 0.6 wt%. In still another aspect, the thermal stabilizer is present in an amount from about 0.1 wt% to about 0.5 wt%. In still another aspect, the thermal stabilizer is present in an amount from about 0.1 wt% to about 0.4 wt%. In still another aspect, the thermal stabilizer is present in an amount from about 0.05 wt% to about 1.0 wt%.
  • plasticizers such as dioctyl-4,5-epoxy-hexahydrophthalate; tris(octoxycarbonylethyl)isocyanurate; tristearin; di- or polyfunctional aromatic phosphates such as resorcinol tetraphenyl diphosphate (RDP), the bis(diphenyl)phosphate of
  • hydroquinone and the bis(diphenyl)phosphate of bisphenol-A poly-alpha-olefms; epoxidized soybean oil; silicones, including silicone oils; esters, for example, fatty acid esters such as alkyl stearyl esters, e.g. methyl stearate; stearyl stearate, pentaerythritol tetrastearate, and the like; mixtures of methyl stearate and hydrophilic and hydrophobic nonionic surfactants comprising polyethylene glycol polymers, polypropylene glycol polymers, and copolymers thereof; waxes such as beeswax, montan wax, paraffin wax or the like.
  • Blended thermoplastic composition additives such as plasticizers, lubricants, and/or mold release agents additive are generally used in amounts of about 0.01 wt% to about 20 wt%, optionally about 0.5 wt% to about 10 wt% the polycarbonate blend composition.
  • the mold release agent is methyl stearate; stearyl stearate or pentaerythritol tetrastearate. In another aspect, the mold release agent is pentaerythritol tetrastearate.
  • the mold release agent is present in an amount from about 0.01 wt% to about 3.0 wt%. In another aspect, the mold release agent is present in an amount from about 0.01 wt% to about 2.5 wt%. In still another aspect, the mold release agent is present in an amount from about 0.5 wt% to about 2.5 wt%. In still another aspect, the mold release agent is present in an amount from about 0.5 wt% to about 2.0 wt%. In still another aspect, the mold release agent is present in an amount from about 0.1 wt% to about 0.6 wt%. In still another aspect, the mold release agent is present in an amount from about 0.1 wt% to about 0.5 wt%.
  • the anti-drip agents can also be present.
  • the anti-drip agent is a styrene-acrylonitrile copolymer encapsulated polytetrafluoroethylene.
  • Exemplary anti-drip agents can include a fibril forming or non- fibril forming fluoropolymer such as polytetrafluoroethylene (PTFE).
  • PTFE polytetrafluoroethylene
  • the anti-drip agent can optionally be encapsulated by a rigid copolymer, for example styrene-acrylonitrile (SAN).
  • SAN styrene-acrylonitrile
  • Encapsulated fluoropolymers can be made by polymerizing the encapsulating polymer in the presence of the fluoropolymer, for example, in an aqueous dispersion.
  • TSAN can provide significant advantages over PTFE, in that TSAN can be more readily dispersed in the composition.
  • a suitable TSAN can comprise, for example, about 50 wt % PTFE and about 50 wt % SAN, based on the total weight of the encapsulated
  • the fluoropolymer can be pre -blended in some manner with a second polymer, such as for, example, an aromatic polycarbonate resin or SAN to form an agglomerated material for use as an anti-drip agent. Either method can be used to produce an encapsulated fluoropolymer.
  • the anti-drip agent is present in an amount from about 0.01 wt% to about 3 wt%. In a still further aspect, the anti-drip agent is present in an amount from about 0.01 wt% to about 2.5 wt%. In yet a further aspect, the anti-drip agent is present in an amount from about 0.5 wt% to about 2.0 wt%.
  • the polycarbonate blend compositions of the present invention can further comprise an acid or an acid salt.
  • the acid or acid salt is an inorganic acid or inorganic acid salt.
  • the acid is an acid including a phosphorous containing oxy-acid.
  • the phosphorous containing oxy-acid is a multi-protic phosphorus containing oxy-acid having the general formula:
  • acids of the foregoing formula include, but are not limited to, acids represented by the following formulas: H 3 PO 4 , H 3 PO 3 , and H 3 PO 2 .
  • Other exemplary acids include phosphoric acid, phosphorous acid, hypophosphorous acid, hypophosphoric acid, phosphinic acid, phosphonic acid,
  • metaphosphoric acid metaphosphoric acid, hexametaphosphoric acid, thiophosphoric acid, fluorophosphoric acid, difluorophosphoric acid, fluorophosphorous acid, difluorophosphorous acid,
  • acids and acid salts such as, for example, sulphuric acid, sulphites, mono zinc phosphate, mono calcium phosphate, sodium acid pyrophosphate, mono natrium phosphate, and the like, can be used.
  • the acid or acid salt is selected so that it can be effectively combined with the mineral filler to produce a synergistic effect and a balance of properties, such as flow and impact, in the polycarbonate or polycarbonate blend.
  • the weight ratio of acid to mineral filler component, or acid:mineral filler component weight ratio can be from about 0.001 to about 0.04.
  • the composition has improved impact properties.
  • the improved impact properties may be seen at low temperatures.
  • the improved impact properties allow the composition to have reduced cracking upon impact.
  • the molded parts have an average notched Izod energy at 23°C ranging from 700 to 900 J/m and a % ductility of 100% according to ASTM D256-2010, for the black blends, and ranging from 600 to 800 J/m and a % ductility of 100% according to ASTM D256-2010, for the white blends.
  • the molded parts have an average notched Izod energy at -30 °C ranging from 600 to 800 J/m and a % ductility of 100% according to ASTM D256-2010, for the black blends, and ranging from 450 to 650 J/m °C and a % ductility of 100% according to ASTM D256-2010, for the white blends.
  • the molded parts have an average notched Izod energy at -40 °C of 550 to 750 J/m and a % ductility of 100% according to ASTM D256-2010, for black blends.
  • the molded parts have an average notched Izod energy at -40 °C of 450 to 650 J/m and a % ductility of 100% according to ASTM D256-2010, for white blends.
  • the molded parts have an average notched Izod energy at -50 °C of 500 to 700 J/m and a % ductility of 100% according to ASTM D256-2010, for black blends.
  • the molded parts have an average notched Izod energy at -50 °C of 150 to 600 J/m and a % ductility of 100% according to ASTM D256-2010, for white blends.
  • the molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod energy at -40 °C of 700 J/m or greater and a ductility of 100% according to ASTM D256-2010.
  • the a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -30 °C of 650 J/m or greater and a % ductility of 100% according to ASTM D256-2010.
  • the molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -40 °C of 500 J/m or greater and a % ductility of 100% according to ASTM D256-2010.
  • the molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -50 °C of 500 J/m or greater and a % ductility of 80% according to ASTM D256-2010.
  • the composition has an average melt flow rate (MFR) of 7 or greater at 300 °C/1.2 kg. In at least one aspect, the composition has an average MFR ranging from 7 to 20 at 300 °C/1.2 kg. In a further aspect, the composition has an average MFR ranging from 7 to 15 at 300 °C/1.2 kg, for example ranging from 7 to 11 at 300 °C/1.2 kg-
  • the percent light transmission ranges from 73 to 85% and the percent haze ranges from 2 to 12%, when the thickness is 3.2mm
  • the composition has a deep black color capability.
  • the deep black color capability is shown by L* (D65 ilium, lOdeg, specular component included).
  • the L* is measured using CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode.
  • the deep black color capability, L* is less than 27.0.
  • the deep black color capability L* ranges from 1 to 27.0.
  • the deep black color capability L* ranges from 10 to 27.0.
  • the deep black color capability L* ranges from 20 to 27.0.
  • the deep black color capability L* ranges from 10 to 20.
  • the deep black color capability L* ranges from 25 to 29.
  • the deep black color capability L* ranges from 26 to 28.
  • the composition has a deep black color capability.
  • the deep black color capability is shown by L* (D65 ilium, lOdeg, specular component included).
  • the L* is measured using CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode.
  • the deep black color capability, L* is less than 28.0.
  • the deep black color capability L* ranges from 1 to 28.0.
  • the deep black color capability L* ranges from 10 to 28.0.
  • the deep black color capability L* ranges from 20 to 28.0.
  • the deep black color capability L* ranges from 10 to 20.
  • the deep black color capability L* ranges from 26 to 30.
  • the deep black color capability L* ranges from 27 to 29.
  • the composition has a bright white color capability.
  • the bright white color capability is shown by L* (D65 ilium, lOdeg, specular component included).
  • the L* is measured using CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode.
  • the bright white color capability L* is greater than 97.0.
  • the bright white color capability L* is greater than 98.0.
  • the bright white color capability L* ranges from 95 to 99.
  • the bright white color capability L* ranges from 97 to 99.
  • the bright white color capability L* ranges from 97.0 to 98.5.
  • the polycarbonate blend compositions of the present invention can be blended with the aforementioned ingredients by a variety of methods involving intimate admixing of the materials with any additional additives desired in the formulation. Because of the availability of melt blending equipment in commercial polymer processing facilities, melt processing methods are generally preferred. Illustrative examples of equipment used in such melt processing methods include: co-rotating and counter-rotating extruders, single screw extruders, co-kneaders, disc-pack processors and various other types of extrusion equipment. The temperature of the melt in the present process is preferably minimized in order to avoid excessive degradation of the resins.
  • melt processed composition exits processing equipment such as an extruder through small exit holes in a die.
  • processing equipment such as an extruder through small exit holes in a die.
  • the resulting strands of molten resin are cooled by passing the strands through a water bath.
  • the cooled strands can be chopped into small pellets for packaging and further handling.
  • compositions can be manufactured by various methods, including batch or continuous techniques that employ kneaders, extruders, mixers, and the like.
  • the composition can be formed as a melt blend employing a twin-screw extruder.
  • at least some of the components are added sequentially.
  • the polycarbonate polymer, the first polysiloxane-polycarbonate component, the second polysiloxane-polycarbonate component, and the colorant composition can be added to the extruder at the feed throat or in feeding sections adjacent to the feed throat, or in feeding sections adjacent to the feed throat, while the various composition additives, e.g.
  • antioxidants and/or a mold release agent can be added to the extruder in a subsequent feeding section downstream.
  • the sequential addition of the components may be accomplished through multiple extrusions.
  • a composition may be made by preextrusion of selected components, such as the polycarbonate polymer, the first polysiloxane-polycarbonate component, the second polysiloxane-polycarbonate component, and the colorant composition to produce a pelletized mixture.
  • a second extrusion can then be employed to combine the preextruded components with any remaining components.
  • Additional composition additives e.g. antioxidants and/or mold release agents, can be added as part of a masterbatch or directly.
  • the composition additives can be added either at the feedthroat or downstream.
  • the extruder can be a two lobe or three lobe twin screw extruder.
  • polysiloxane- " polycarbonate component, the second polysiloxane-polycarbonate component, the colorant composition and/or other optional components are first blended in a
  • HENSCHEL-MixerTM high speed mixer Other low shear processes, including but not limited to hand mixing, can also accomplish this blending.
  • the blend is then fed into the throat of a twin-screw extruder via a hopper.
  • at least one of the components can be incorporated into the composition by feeding directly into the extruder at the throat and/or downstream through a sidestuffer.
  • Additives can also be compounded into a masterbatch with a desired polymeric resin and fed into the extruder.
  • the extruder is generally operated at a temperature higher than that necessary to cause the composition to flow.
  • the extrudate is immediately quenched in a water batch and pelletized.
  • the pellets, so prepared, can be one-fourth inch long or less as desired. Such pellets can be used for subsequent molding, shaping, or forming.
  • the invention relates to methods of preparing a composition, the method comprising the step of mixing a polycarbonate polymer, a first
  • polysiloxane-polycarbonate copolymer a polysiloxane-polycarbonate copolymer, a second polysiloxane-polycarbonate copolymer, and a colorant composition.
  • the invention relates to methods of a preparing a composition, comprising the step of mixing: (a) a polycarbonate homopolymer; (b) a first
  • polysiloxane-polycarbonate copolymer comprising: (i) poly diorganosiloxane blocks comprising repeating structural units of formula:
  • polydiorganosiloxane block length (E) is from 30 to 60; and (ii) polycarbonate blocks comprising polycarbonate units of formula: wherein at least 60 percent of the total number of R groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the first polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 4 to 8 wt % diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer; (c) a second polysiloxane-polycarbonate copolymer comprising: (i)
  • polydiorganosiloxane blocks comprising repeating structural units of formula:
  • polydiorganosiloxane block length (E) is from 30 to 100; and (ii) polycarbonate blocks comprising polycarbonate units of formula:
  • the blend composition has an average melt flow rate (MFR) of 7 or greater measured at 300 °C/1.2 kg; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has a black color characterized by an average L* value of 27 or less as measured by the CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -30 °C of 650 J/m or greater and a % ductility of 100% according to ASTM D256-2010.
  • MFR average melt flow rate
  • the invention relates to methods of a preparing a composition, comprising the step of mixing: (a) from 15 wt% to 30 wt% of a polycarbonate
  • a first polysiloxane-polycarbonate copolymer comprising: (i) polydiorganosiloxane blocks comprising repeating structural units of formula: wherein the polydiorganosiloxane block length (E) is from 30 to 60; and (ii) polycarbonate blocks comprising polycarbonate units of formula: wherein at least 60 percent of the total number of R 1 groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the first polysiloxane -polycarbonate copolymer comprises a diorganosiloxane content of from 4 to 8 wt % diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer; (c) from greater than 0 wt% to 8 wt% of a second polysiloxane-polycarbonate
  • polydiorganosiloxane block length (E) is from 30 to 100; and (ii) polycarbonate blocks comprising polycarbonate units of formula: wherein at least 60 percent of the total number of R 1 groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the second polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 15 to 30 wt % diorganosiloxane based on the total weight of the second
  • polysiloxane-polycarbonate copolymer and (d) a colorant composition; wherein the total weight percent wherein the total weight percent is relative to the polycarbonate polymer, first polysiloxane -polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer blend composition has an average melt flow rate (MFR) of 7 or greater measured at
  • a molded part having a thickness of 3.2 mm formed from the blend composition has a black color characterized by an average L* value of 27 or less as measured by the CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -30 °C of 650 J/m or greater and a % ductility of 100% according to ASTM D256-2010.
  • the invention relates to methods of a preparing a composition, comprising the step of mixing: (a) from 15 wt% to 45 wt% of a polycarbonate
  • polydiorganosiloxane block length (E) is from 30 to 60; and (ii) polycarbonate blocks comprising polycarbonate units of formula:
  • the first polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 4 to 8 wt % diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer; (c) from greater than 0 wt% to 8 wt% of a second polysiloxane-polycarbonate copolymer comprising: (i) polydiorganosiloxane blocks comprising repeating structural units of formula:
  • polydiorganosiloxane block length (E) is from 30 to 100; and (ii) polycarbonate blocks comprising polycarbonate units of formula: wherein at least 60 percent of the total number of R groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the second polysiloxane -polycarbonate copolymer comprises a diorganosiloxane content of from 15 to 30 wt % diorganosiloxane based on the total weight of the second
  • polysiloxane -polycarbonate copolymer comprising (d) a colorant composition; wherein the total weight percent wherein the total weight percent is relative to the polycarbonate polymer, first polysiloxane -polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer blend composition has an average melt flow rate (MFR) of 7 or greater measured at
  • a molded part having a thickness of 3.2 mm formed from the blend composition has a black color characterized by an average L* value of 27 or less as measured by the CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -30 °C of 650 J/m or greater and a % ductility of 100% according to ASTM D256-2010.
  • the composition may be used as part of a method for reducing cracking because of its impact properties.
  • a method for reducing the rate of cracking of an electronic housing comprising: a) providing the composition, disclosed above; b) molding said electronic housing; and c) applying stress to said housing.
  • the electronic housing may be housing for a cell phone or smart phone.
  • a method of making a housing to reduce the rate of cracking comprising: a) providing the composition, disclosed above; b) molding the composition, disclosed above; c) hard coating the composition with a hard coat that is less than or equal to 13 microns; and d) drilling one or more apertures in said molded housing.
  • the method may be used to prepare housing for a gaming system, a cell phone, a smart phone, a GPS device, a laptop computer, a tablet computer, an e- reader, a copier, a sports goggle, or an eyeglass frame.
  • the molding and the hard coating performed in the method may be done using standard techniques.
  • the aperture drilling may be performed using standard techniques.
  • the reduced rate of cracking may be seen by the impact properties.
  • the improved impact strength may show a reduced rate of cracking. In other words, this relationship may be illustrated by the greater the impact strength, the smaller the rate of cracking.
  • the impact strength may be shown by the average notched Izod energy, for example according to the ASTM D256-2010.
  • the impact strength or properties may also be shown by other standard tests used to measure impact properties.
  • the hard coating may have a hard coat that is less than or equal to 13 microns.
  • the hard coating may have a hard coat that is less than or equal to 10 microns.
  • the hard coating may have a hard coat that is less than or equal to 7 microns.
  • the resulting composite mixture can be used to provide any desired shaped, formed, or molded articles.
  • the composite mixture may be molded into useful shaped articles by a variety of means such as injection molding, extrusion, rotational molding, blow molding and thermoforming.
  • the disclosed composites are particularly well suited for use in the manufacture of electronic components and devices.
  • the disclosed composites can be used to form articles such as printed circuit board carriers, burn in test sockets, flex brackets for hard disk drives, and the like.
  • the present invention pertains to shaped, formed, or molded articles comprising the polycarbonate blend compositions.
  • the polycarbonate blend compositions can be molded into useful shaped articles by a variety of means such as injection molding, extrusion, rotational molding, blow molding and thermoforming to form articles.
  • the polycarbonate blend compositions described herein can also be made into film and sheet as well as components of laminate systems.
  • a method of manufacturing an article comprises melt blending the polycarbonate polymer, the first polysiloxane -polycarbonate component, the second polysiloxane -polycarbonate component, and the colorant composition; and molding the extruded composition into an article.
  • the extruding is done with a twin-screw extruder.
  • the article is an injection molded article.
  • the article is an extruded film or sheet.
  • the composition may be formed into the article, film, or sheet using conventional methods.
  • the article has a thickness less than 1.5 mm.
  • the article, film, or sheet may be used to form an apparatus.
  • the article may have one or more apertures.
  • the article is a component for an electronic device.
  • the electronic device is selected from a gaming system, a cell phone, a smart phone, a GPS device, a laptop computer, a tablet computer, an e- reader, a copier.
  • the article is a component for a sports goggle or an eyeglass frame.
  • the article may be a component of a smart phone.
  • formed articles include, for example, personal computers, notebook and portable computers, cell phone antennas and other such items.
  • the article is a computer and business machine housing such as a housing for high end laptop personal computers, monitors, a hand held electronic device housing such as a housing for smart phones, tablets, music devices electrical connectors, and components of lighting fixtures, ornaments, home appliances, and the like.
  • the present invention pertains to electrical or electronic devices comprising the disclosed polycarbonate blend compositions.
  • the electrical or electronic device comprising the disclosed polycarbonate blend compositions is a cellphone, a MP3 player, a computer, a laptop, a camera, a video recorder, an electronic tablet, a pager, a hand receiver, a video game, a calculator, a wireless car entry device, an automotive part, a filter housing, a luggage cart, an office chair, a kitchen appliance, an electrical housing, an electrical connector, a lighting fixture, a light emitting diode, an electrical part, or a telecommunications part.
  • the polymer composition can be used in the field of electronics.
  • fields which can use the disclosed blended thermoplastic polymer compositions include electrical, electro-mechanical, radio frequency (PvF) technology, telecommunication, automotive, aviation, medical, sensor, military, and security.
  • PvF radio frequency
  • the use of the disclosed blended thermoplastic polymer compositions can also be present in overlapping fields, for example in mechatronic systems that integrate mechanical and electrical properties which may, for example, be used in automotive or medical engineering.
  • PA2 Phosphorous acid powder mixture of 0.62% of phosphorous
  • UV UV absorber from the benzotriazole class with the chemical
  • PETS Release agent pentaerythritoltetrastearate; available under the trade name Glycolube P (Lonza).
  • Table 2a shows the compositions in solvent black color.
  • Table 2b shows the compositions in bright white color.
  • siloxane percentage equals 4.98 w%, meaning that the siloxane percentage is held constant.
  • Table 2a Compositions in solvent black color in weight percentage.
  • Table 2b Compositions in bright white color in weight percentage.
  • compositions were compounded in a ZSK 30 mm co-rotating twin screw extruder using a melt temperature of 300 °C with a rate of 20 kgs/hr, and 20 inches of mercury vacuum and a screw speed of 400 RPM.
  • the extrudate was cooled under water, pelletized and dried at 120 °C for four hours with a desiccant bed dryer.
  • the dried pellets were injection molded using a Van Dorn 80T molding machine at 300 °C melt temperature to form test parts for impact and mechanical testing. Physical and mechanical properties of the test materials were measured using ASTM and ISO test standards.
  • Table 3 shows the impact data for the compositions in solvent black color.
  • Table 4 shows the impact property data for the compositions in bright white color.
  • Measured on a molded part having a thickness of 3.2 mm formed from the indicated blend composition has a black color characterized by an averag value of 27 or less as measured by the CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode.
  • melt volume rate MVR
  • compositions comprising about 4.0 wt% PCPS2 loading (BK-6 to BK-10) and at about 5.0 wt% PCPS2 loading (BK-11 to BK-14) have 80-100 % ductility at -30°C. Deep black colors (L* ⁇ 28.0) are only achieved at these PCPS2 loadings (4.0-5.0 wt%) when greater than about 50 wt% of PCPSl is present in the composition (BK-6, BK-7. BK-8, BK-11 and BK-12). In contrast, the compositions comprising less than about 50 wt% of PCPSl (BK-9, BK-10, BK-13 and BK-14) are not capable of achieving a deep black color (L* > 28.0).
  • Embodiment 1 A polycarbonate blend composition comprising: a polycarbonate polymer; a first polysiloxane-polycarbonate copolymer comprising:
  • polydiorganosiloxane block length (E) is from 30 to 60; and polycarbonate blocks comprising polycarbonate units of formula:
  • R 1 groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties;
  • first polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 4 to 8 wt % diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer; b. a second polysiloxane-polycarbonate copolymer comprising: i. polydiorganosiloxane blocks comprising repeating structural units of formula:
  • polydiorganosiloxane block length (E) is from 30 to 100; and ii. polycarbonate blocks comprising polycarbonate units of formula:
  • a colorant composition wherein the blend composition has an average melt flow rate (MFR) of 7 or greater measured at 300 °C/1.2 kg; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has a black color characterized by an average L* value of 27 or less as measured by the CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -30 °C of 650 J/m or greater and a % ductility of 100% according to ASTM D256-2010; and wherein R is the same or different, and is a C 1-13 monovalent organic group; R 2 is independently a divalent Ci-C 30 organic group; M is independently a halogen, cyano, nitro, Ci-Cg alkylthio, Ci-Cg alkyl, Ci-Cg alkoxy, C 2
  • Embodiment 2 The composition of Embodiment 1, wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod energy at -40 °C of 700 J/m or greater and a % ductility of 100% according to ASTM D256-2010.
  • Embodiment 3 The composition of Embodiments 1 or 2, wherein the colorant composition comprises less than 1.5 wt % of an inorganic colorant based on the total weight of the colorant composition.
  • Embodiment 4 The composition of any of Embodiments 1-3, wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod energy at -50 °C of 700 J/m or greater and a % ductility of 100% according to ASTM D256-2010.
  • Embodiment 5 The composition of any of Embodiments 1-4, wherein the second polysiloxane-polycarbonate copolymer is present in the blend composition in an amount of about 2.5 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
  • Embodiment 6 The composition of any of Embodiment 1-5, wherein the polycarbonate polymer is present in an amount in the range of from 15 wt% to 30 wt% relative to the total weight percent of the polycarbonate polymer, first
  • polysiloxane-polycarbonate copolymer and second polysiloxane-polycarbonate copolymer.
  • Embodiment 7 The composition of any of Embodiment 1-5, wherein the polycarbonate polymer is present in an amount in the range of from 22 wt% to 29 wt% relative to the total weight percent of the polycarbonate polymer, first
  • polysiloxane-polycarbonate copolymer and second polysiloxane-polycarbonate copolymer.
  • Embodiment 8 The composition of any of Embodiments 1-7, wherein the polycarbonate polymer comprises a blend of at least two polycarbonate polymers.
  • Embodiment 9 The composition of Embodiment 8, wherein the polycarbonate polymer comprises a first polycarbonate polymer and a second polycarbonate polymer.
  • Embodiment 10 The composition of Embodiment 9, wherein the first
  • polycarbonate polymer is a low flow polycarbonate.
  • Embodiment 11 The composition of Embodiment 8 or 9, wherein the second polycarbonate polymer is a high flow polycarbonate.
  • Embodiment 12 The composition of Embodiment 9-11 , wherein the first polycarbonate polymer is present in an amount in the range of from 11 wt% to 29 wt% relative to the total weight percent of the polycarbonate polymer, first
  • polysiloxane-polycarbonate copolymer and second polysiloxane-polycarbonate copolymer and wherein the second polycarbonate polymer is present in an amount in the range of from greater than 0 wt% to 8 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
  • Embodiment 13 The composition of Embodiment 9-11 , wherein the first polycarbonate polymer is present in an amount in the range of from 14 wt% to 29 wt% relative to the total weight percent of the polycarbonate polymer, first
  • polysiloxane-polycarbonate copolymer and second polysiloxane-polycarbonate copolymer and wherein the second polycarbonate polymer is present in an amount in the range of from greater than 0 wt% to 8 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
  • Embodiment 14 The composition of any of Embodiments 1-13, wherein the total combined weight percent of the first and second polysiloxane-polycarbonate copolymers present in the blend composition is in the range of from 70 wt% to 80 wt% relative to the total combined weight percent of the polycarbonate polymer, first
  • polysiloxane-polycarbonate copolymer and second polysiloxane-polycarbonate copolymer.
  • Embodiment 15 The composition of any of Embodiments 1-14, wherein the first polysiloxane-polycarbonate copolymer is present in an amount in the range of from 65 wt% to 75 wt% relative to the total combined weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
  • Embodiment 16 The composition of any of Embodiments 1-15, wherein the second polysiloxane-polycarbonate copolymer is present in an amount in the range of from greater than 0 wt% to 5 wt% relative to the total combined weight percent of the
  • polycarbonate polymer first polysiloxane-polycarbonate copolymer, and second
  • Embodiment 17 The composition of any of Embodiments 1-16, wherein the total weight percentage of siloxane ranges from 4.5 wt % to 5.5 wt % based on the total combined weight of the first polysiloxane-polycarbonate, second polysiloxane-polycarbonate, and the polycarbonate.
  • Embodiment 18 The composition of any of Embodiments 1-17, wherein the absence of colorants, the percent light transmission ranges from 73 to 85% and the percent haze ranges from 2 to 12%, when the thickness is 3.2mm.
  • Embodiment 19 A polycarbonate blend composition comprising:
  • a first polysiloxane-polycarbonate copolymer comprising: i. polydiorganosiloxane blocks comprising repeating structural units of formula:
  • polydiorganosiloxane block length (E) is from 30 to 60; and ii. polycarbonate blocks comprising polycarbonate units of formula: wherein at least 60 percent of the total number of R 1 groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the first polysiloxane-polycarbonate copolymer comprises a
  • diorganosiloxane content of from 4 to 8 wt % diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer; a second polysiloxane-polycarbonate copolymer comprising: i. polydiorganosiloxane blocks comprising repeating structural units of formula:
  • polydiorganosiloxane block length (E) is from 30 to 100; and ii. polycarbonate blocks comprising polycarbonate units of formula: O
  • a colorant composition wherein the blend composition has an average melt flow rate (MFR) of 7 or greater measured at 300 °C/1.2 kg; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has a black color characterized by an average L* value of 28 or less as measured by the CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -30 °C of 600 J/m or greater and a % ductility of 80% according to ASTM D256-2010; and wherein R is the same or different, and is a C 1-13 monovalent organic group; R 2 is independently a divalent C 1 -C30 organic group; M is independently a halogen, cyano, nitro, Ci-Cg alkylthio, Ci-Cg alkyl, Ci-Cg alkoxy, C
  • a polycarbonate polymer g. a polycarbonate polymer; h. a first polysiloxane-polycarbonate copolymer comprising: i. polydiorganosiloxane blocks comprising repeating structural units of formula:
  • polydiorganosiloxane block length (E) is from 30 to 60; and ii. polycarbonate blocks comprising polycarbonate units of formula:
  • diorganosiloxane content of from 4 to 8 wt % diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer; a second polysiloxane-polycarbonate copolymer comprising: i. polydiorganosiloxane blocks comprising repeating structural units of formula:
  • polydiorganosiloxane block length (E) is from 30 to 100; and ii. polycarbonate blocks comprising polycarbonate units of formula: O
  • a colorant composition wherein the blend composition has an average melt flow rate (MFR) of 7 or greater measured at 300 °C/1.2 kg; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has a black color characterized by an average L* value of 28 or less as measured by the CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -30 °C of 600 J/m or greater and a % ductility of 80% according to ASTM D256-2010; and wherein R is the same or different, and is a C 1-13 monovalent organic group; R 2 is independently a divalent C 1 -C30 organic group; M is independently a halogen, cyano, nitro, Ci-Cg alkylthio, Ci-Cg alkyl, Ci-Cg alkoxy, C
  • Embodiment 21 The composition of Embodiments 19 or 20, wherein the colorant composition comprises less than 12 wt % of an inorganic colorant based on the total weight of the colorant composition.
  • Embodiment 22 The composition of any of Embodiments 19-21 , wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod energy at -40 °C of 500 J/m or greater and a % ductility of 100% according to ASTM D256-2010.
  • Embodiment 23 The composition of any of Embodiments 19-22, wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod energy at -50 °C of 500 J/m or greater and a % ductility of 80% according to ASTM D256-2010.
  • Embodiment 24 The composition of any of Embodiments 20-23, wherein the polycarbonate polymer is present in an amount in the range of from 0 wt% to 55 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
  • Embodiment 25 The composition of any of Embodiments 20-24, wherein the polycarbonate polymer is present in an amount in the range of from 0 wt% to 45 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
  • Embodiment 26 The composition of any of Embodiments 20-25, wherein the polycarbonate polymer comprises a blend of at least two polycarbonate polymers.
  • Embodiment 27 The composition of Embodiment 26, wherein the
  • polycarbonate polymer comprises a first polycarbonate polymer and a second polycarbonate polymer.
  • Embodiment 28 The composition of Embodiment 27, wherein the first polycarbonate polymer is a low flow polycarbonate.
  • Embodiment 29 The composition of Embodiment 27 or 28, wherein the second polycarbonate polymer is a high flow polycarbonate.
  • Embodiment 30 The composition of any of Embodiments 27-29, wherein the first polycarbonate polymer is present in an amount in the range of from 10 wt% to 30 wt% relative to the total weight percent of the polycarbonate polymer, first
  • polysiloxane-polycarbonate copolymer and second polysiloxane-polycarbonate copolymer and wherein the second polycarbonate polymer is present in an amount in the range of from greater than 0 wt% to 15 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second
  • Embodiment 31 The composition of any of Embodiments 19-30, wherein the total combined weight percent of the first and second polysiloxane-polycarbonate copolymers present in the blend composition is in the range of from 54 wt% to 100 wt% relative to the total combined weight percent of the polycarbonate polymer, first
  • polysiloxane-polycarbonate copolymer and second polysiloxane-polycarbonate copolymer.
  • Embodiment 32 The composition of any of Embodiments 19-31, wherein the first polysiloxane-polycarbonate copolymer is present in an amount in the range of from 50 wt% to 95 wt% relative to the total combined weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
  • Embodiment 33 The composition of any of Embodiments 19-32, wherein the second polysiloxane-polycarbonate copolymer is present in an amount in the range of from greater than 0 wt% to 5 wt% relative to the total combined weight percent of the
  • polycarbonate polymer first polysiloxane-polycarbonate copolymer, and second
  • Embodiment 34 The composition of any of Embodiments 19-33, wherein the total weight percentage of siloxane ranges from 4.0 wt % to 7 wt % based on the total combined weight of the first polysiloxane-polycarbonate, second polysiloxane-polycarbonate, and the polycarbonate.
  • Embodiment 35 The composition of any of Embodiments 19-34, wherein the absence of colorants, the percent light transmission ranges from 65 to 85% and the percent haze ranges from 2 to 25%, when the thickness is 3.2 mm.
  • Embodiment 36 The composition of any of Embodiments 19-35, wherein the second polysiloxane-polycarbonate copolymer is present in the blend composition in an amount of about 4 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
  • Embodiment 37 The composition of any of Embodiments 1-36, wherein the second polysiloxane-polycarbonate copolymer is present in the blend composition in an amount less than 5 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
  • Embodiment 38 The composition of any of Embodiments 1-37, wherein the first polysiloxane-polycarbonate copolymer has an weight-averaged molecular weight, Mw, in the range of from 20,000 to 25,000 and wherein an injection molded part having a thickness of 3.2 mm formed from the blend composition has an average haze of less than 2.5 % measured according to ASTM D1003.
  • Embodiment 39 The composition of any of Embodiments 1-38, wherein the second polysiloxane-polycarbonate copolymer has a weight-averaged molecular weight, Mw, in the range of from 25,000 to 35,000.
  • Embodiment 40 The composition of any of Embodiments 1-18 and 20-39, wherein the polycarbonate polymer is a Bisphenol-A -polycarbonate.
  • Embodiment 41 The composition of Embodiment 40, wherein the Bisphenol-A polycarbonate has a weight-averaged molecular weight between 18,000 and 32,000.
  • Embodiment 42 The composition of Embodiment 40, wherein the Bisphenol-A polycarbonate has a weight-averaged molecular weight between 28,000 and 32,000.
  • Embodiment 43 The composition of any of Embodiments 1-42, wherein the siloxane units of the first and second polysiloxane polycarbonate copolymers are
  • Embodiment 44 The composition of any of Embodiments 1-43, wherein the polydiorganosiloxane has moieties derived from eugenol, 4-allylphenol or 2-allylphenol.
  • Embodiment 45 The composition of any of Embodiments 1-44, wherein the colorant composition comprises carbon black in an amount less than 1.5 wt % of the total colorant composition.
  • Embodiment 46 The composition of any of Embodiments 1-45, wherein the PDI of the first polysiloxane-polycarbonate and the second polysiloxane-polycarbonate ranges from 2 to 3.
  • Embodiment 47 The composition of any of Embodiments 1-46, wherein the first polysiloxane-polycarbonate and the second polysiloxane-polycarbonate comprise a polycarbonate unit derived from bisphenol-A.
  • Embodiment 48 An article of manufacture formed from the blend composition of any of Embodiments 1- 47.
  • Embodiment 49 The article of manufacture of Embodiment 48, wherein the thickness of the article is less than 1.5 mm.
  • Embodiment 50 The article of manufacture of Embodiment 48, wherein the thickness of the article is less than 1.5 mm in at least a portion of the article.
  • Embodiment 51 The article of manufacture of any of Embodiments 48-50, wherein the article is an injection molded part.
  • Embodiment 52 The article of manufacture of any of Embodiments 48-50, wherein the article is an extruded film or sheet.
  • Embodiment 53 The article of manufacture of any Embodiments 48-50, wherein the article is a component for an electronic device.
  • Embodiment 54 The article of manufacture of Embodiment 53, wherein the electronic device is selected from a gaming system, a cell phone, a smart phone, a GPS device, a laptop computer, a tablet computer, an e- reader, or a copier.
  • the electronic device is selected from a gaming system, a cell phone, a smart phone, a GPS device, a laptop computer, a tablet computer, an e- reader, or a copier.
  • Embodiment 55 The article of manufacture of any of Embodiments 48-50, wherein the article is a component for a sports goggle or an eyeglass frame.

Abstract

The present disclosure describes polycarbonate-siloxane blends with a constant percentage of siloxane in the formulations. The polycarbonate-siloxane blends achieve improved impact properties, as well as the ability to achieve deep black and bright white colors.

Description

IMPROVED LOW TEMPERATURE IMPACT PROPERTIES IN PC-SILOXANE COPOLYMER BLEND WITH BLACK AND WHITE COLOR CAPABILITY
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This Application claims the benefit of U.S. Provisional Application No.
61/695,231, filed on August 30, 2012, and U.S. Provisional Application No. 61/695,550, filed on August 31, 2012, which are both incorporated herein by reference in its entirety.
BACKGROUND OF THE INVENTION
[0002] Previous products using standard polycarbonates do not have sufficient impact strength to reduce the rate of cracking. The standard polycarbonates also do not have the ability to achieve a deep black color and bright white colors.
[0003] Accordingly, there remains a need for compositions that have good impact properties with the ability to achieve deep black and bright white colors. This and other needs are satisfied by the various aspects of the present disclosure.
SUMMARY OF THE INVENTION
[0004] This invention relates generally to a composition with good impact properties. To that end, according to the aspects, compositions are disclosed that generally comprise a blend a polycarbonate polymer with a first polysiloxane-polycarbonate copolymer, a second polysiloxane-polycarbonate copolymer, and a color composition.
[0005] The present disclosure describes a composition with a constant percentage of siloxane in the formulations. The composition achieves improved impact properties, as well as the ability to achieve deep black and bright white colors.
[0006] In one aspect, the present disclosure describes a polycarbonate blend composition comprising: (a) a polycarbonate homopolymer; (b) a first polysiloxane-polycarbonate copolymer comprising: (i) polydiorganosiloxane blocks comprising repeating structural units of formula:
Figure imgf000002_0001
wherein the polydiorganosiloxane block length (E) is from 30 to 60; and (ii) polycarbonate blocks comprising polycarbonate units of formula: O
R1— O C O wherein at least 60 percent of the total number of R1 groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the first polysiloxane -polycarbonate copolymer comprises a diorganosiloxane content of from 4 to 8 wt % diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer; (c) a second polysiloxane-polycarbonate copolymer comprising: (i)
polydiorganosiloxane blocks comprising repeating structural units of formula:
Figure imgf000003_0001
wherein the polydiorganosiloxane block length (E) is from 30 to 100; and (ii) polycarbonate blocks comprising polycarbonate units of formula:
O
R1— O C O wherein at least 60 percent of the total number of R1 groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the second polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 15 to 30 wt % diorganosiloxane based on the total weight of the second
polysiloxane-polycarbonate copolymer; and (d) a colorant composition; wherein the blend composition has an average melt flow rate (MFR) of 7 or greater measured at 300 °C/1.2 kg; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has a black color characterized by an average L* value of 27 or less as measured by the CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -30 °C of 650 J/m or greater and a % ductility of 100% according to ASTM D256-2010.
[0007] According to further aspects, disclosed are compositions that have an improved notched Izod impact strength that does not comprise the other properties of the composition. [0008] In further aspects, disclosed are articles comprising the disclosed composition, for example an article as a component in a smart phone.
[0009] In a further aspect, the invention relates to methods of making the disclosed compositions.
[0010] Other advantages will be set forth in part in the description which follows or may be learned by practice. The advantages will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive, as claimed.
DETAILED DESCRIPTION OF THE INVENTION
[0011] The present invention can be understood more readily by reference to the following detailed description, examples, drawings, and claims, and their previous and following description. However, before the present compositions, articles, devices, systems, and/or methods are disclosed and described, it is to be understood that this invention is not limited to the specific compositions, articles, devices, systems, and/or methods disclosed unless otherwise specified, as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting.
[0012] The following description of the invention is also provided as an enabling teaching of the invention in its best, currently known aspect. To this end, those of ordinary skill in the relevant art will recognize and appreciate that changes and modifications can be made to the various aspects of the invention described herein, while still obtaining the beneficial results of the present invention. It will also be apparent that some of the desired benefits of the present invention can be obtained by selecting some of the features of the present invention without utilizing other features. Accordingly, those of ordinary skill in the relevant art will recognize that many modifications and adaptations to the present invention are possible and can even be desirable in certain circumstances and are thus also a part of the present invention. Thus, the following description is provided as illustrative of the principles of the present invention and not in limitation thereof.
[0013] Various combinations of elements of this disclosure are encompassed by this invention, e.g. combinations of elements from dependent claims that depend upon the same independent claim.
[0014] Moreover, it is to be understood that unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically stated in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including: matters of logic with respect to arrangement of steps or operational flow; plain meaning derived from grammatical organization or punctuation; and the number or type of aspects described in the specification.
[0015] All publications mentioned herein are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the publications are cited.
[0016] It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. As used in the specification and in the claims, the term "comprising" may include the aspects "consisting of and "consisting essentially of." Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In this specification and in the claims which follow, reference will be made to a number of terms which shall be defined herein.
[0017] As used in the specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a polycarbonate" includes mixtures of two or more such
polycarbonates. Furthermore, for example, reference to a filler includes mixtures of fillers.
[0018] Ranges can be expressed herein as from "about" one particular value, and/or to "about" another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as "about" that particular value in addition to the value itself. For example, if the value "10" is disclosed, then "about 10" is also disclosed. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.
[0019] As used herein, the terms "about" and "at or about" mean that the amount or value in question can be the value designated some other value approximately or about the same. It is generally understood, as used herein, that it is the nominal value indicated ±10% variation unless otherwise indicated or inferred. The term is intended to convey that similar values promote equivalent results or effects recited in the claims. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but can be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art. In general, an amount, size, formulation, parameter or other quantity or characteristic is "about" or "approximate" whether or not expressly stated to be such. It is understood that where "about" is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.
[0020] As used herein, the terms "optional" or "optionally" mean that the subsequently described event, condition, component, or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
[0021] As used herein, the term or phrase "effective," "effective amount," or
"conditions effective to" refers to such amount or condition that is capable of performing the function or property for which an effective amount is expressed. As will be pointed out below, the exact amount or particular condition required will vary from one aspect to another, depending on recognized variables such as the materials employed and the processing conditions observed. Thus, it is not always possible to specify an exact "effective amount" or "condition effective to." However, it should be understood that an appropriate effective amount will be readily determined by one of ordinary skill in the art using only routine experimentation.
[0022] Disclosed are the components to be used to prepare disclosed compositions of the invention as well as the compositions themselves to be used within methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds cannot be explicitly disclosed, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed and a number of modifications that can be made to a number of molecules including the compounds are discussed, specifically contemplated is each and every combination and permutation of the compound and the modifications that are possible unless specifically indicated to the contrary. Thus, if a class of molecules A, B, and C are disclosed as well as a class of molecules D, E, and F and an example of a combination molecule, A-D is disclosed, then even if each is not individually recited each is individually and collectively contemplated meaning combinations, A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are considered disclosed. Likewise, any subset or combination of these is also disclosed. Thus, for example, the sub-group of A-E, B-F, and C-E would be considered disclosed. This concept applies to all aspects of this application including, but not limited to, steps in methods of making and using the compositions of the invention. Thus, if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with any specific aspect or combination of aspects of the methods of the invention.
[0023] References in the specification and concluding claims to parts by weight, of a particular element or component in a composition or article, denotes the weight relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed. Thus, in a composition containing 2 parts by weight of component X and 5 parts by weight component Y, X and Y are present at a weight ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the compound.
[0024] As used herein the terms "weight percent," "wt%," and "wt. %," which can be used interchangeably, indicate the percent by weight of a given component based on the total weight of the composition, unless otherwise specified. That is, unless otherwise specified, all wt% values are based on the total weight of the composition. It should be understood that the sum of wt% values for all components in a disclosed composition or formulation are equal to 100.
[0025] A weight percent of a component, unless specifically stated to the contrary, is based on the total weight of the formulation or composition in which the component is included. For example if a particular element or component in a composition or article is said to have 8% weight, it is understood that this percentage is relation to a total
compositional percentage of 100%.
[0026] Compounds are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valency filled by a bond as indicated, or a hydrogen atom. A dash ("-") that is not between two letters or symbols is used to indicate a point of attachment for a substituent. For example, -CHO is attached through carbon of the carbonyl group. Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this invention belongs. [0027] The term "alkyl group" as used herein is a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like. A "lower alkyl" group is an alkyl group containing from one to six carbon atoms.
[0028] The term "alkoxy" as used herein is an alkyl group bound through a single, terminal ether linkage; that is, an "alkoxy" group can be defined as OR where R is alkyl as defined above. A "lower alkoxy" group is an alkoxy group containing from one to six carbon atoms.
[0029] The term "alkenyl group" as used herein is a hydrocarbon group of from 2 to 24 carbon atoms and structural formula containing at least one carbon-carbon double bond. Asymmetric structures such as (AB)C=C(CD) are intended to include both the E and Z isomers. This can be presumed in structural formulae herein wherein an asymmetric alkene is present, or it can be explicitly indicated by the bond symbol C.
[0030] The term "alkynyl group" as used herein is a hydrocarbon group of 2 to 24 carbon atoms and a structural formula containing at least one carbon-carbon triple bond.
[0031] The term "aryl group" as used herein is any carbon-based aromatic group including, but not limited to, benzene, naphthalene, etc. The term "aromatic" also includes "heteroaryl group," which is defined as an aromatic group that has at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. The aryl group can be substituted or unsubstituted. The aryl group can be substituted with one or more groups including, but not limited to, alkyl, alkynyl, alkenyl, aryl, halide, nitro, amino, ester, ketone, aldehyde, hydroxy, carboxylic acid, or alkoxy.
[0032] The term "cycloalkyl group" as used herein is a non-aromatic carbon-based ring composed of at least three carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. The term
"heterocycloalkyl group" is a cycloalkyl group as defined above where at least one of the carbon atoms of the ring is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulphur, or phosphorus.
[0033] The term "aralkyl" as used herein is an aryl group having an alkyl, alkynyl, or alkenyl group as defined above attached to the aromatic group. An example of an aralkyl group is a benzyl group.
[0034] The term "hydroxyalkyl group" as used herein is an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group described above that has at least one hydrogen atom substituted with a hydroxyl group.
[0035] The term "alkoxyalkyl group" is defined as an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group described above that has at least one hydrogen atom substituted with an alkoxy group described above.
[0036] The term "ester" as used herein is represented by the formula— C(0)OA, where A can be an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl,
cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.
[0037] The term "carbonate group" as used herein is represented by the formula
OC(0)OR, where R can be hydrogen, an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group described above.
[0038] The term "carboxylic acid" as used herein is represented by the formula
C(0)OH.
[0039] The term "aldehyde" as used herein is represented by the formula -C(0)H.
[0040] The term "keto group" as used herein is represented by the formula -C(0)R, where R is an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group described above.
[0041] The term "carbonyl group" as used herein is represented by the formula C=0.
[0042] The term "ether" as used herein is represented by the formula AOA1 , where A and Al can be, independently, an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.
[0043] The term "organic residue" defines a carbon containing residue, i.e., a residue comprising at least one carbon atom, and includes but is not limited to the carbon-containing groups, residues, or radicals defined hereinabove. Organic residues can contain various heteroatoms, or be bonded to another molecule through a heteroatom, including oxygen, nitrogen, sulfur, phosphorus, or the like. Examples of organic residues include but are not limited alkyl or substituted alkyls, alkoxy or substituted alkoxy, mono or di-substituted amino, amide groups, etc. Organic residues can preferably comprise 1 to 18 carbon atoms, 1 to 15, carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. In a further aspect, an organic residue can comprise 2 to 18 carbon atoms, 2 to 15, carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, 2 to 4 carbon atoms, or 2 to 4 carbon atoms.
[0044] A very close synonym of the term "residue" is the term "radical," which as used in the specification and concluding claims, refers to a fragment, group, or substructure of a molecule described herein, regardless of how the molecule is prepared.
2,4-dihydroxyphenyl radical in a particular compound has the structure
Figure imgf000010_0001
regardless of whether 2,4-dihydroxyphenyl is used to prepare the compound. In some aspects the radical (for example an alkyl) can be further modified (i.e., substituted alkyl) by having bonded thereto one or more "substituent radicals." The number of atoms in a given radical is not critical to the present invention unless it is indicated to the contrary elsewhere herein.
[0045] "Organic radicals," as the term is defined and used herein, contain one or more carbon atoms. An organic radical can have, for example, 1-26 carbon atoms, 1-18 carbon atoms, 1-12 carbon atoms, 1-8 carbon atoms, 1-6 carbon atoms, or 1-4 carbon atoms. In a further aspect, an organic radical can have 2-26 carbon atoms, 2-18 carbon atoms, 2-12 carbon atoms, 2-8 carbon atoms, 2-6 carbon atoms, or 2-4 carbon atoms. Organic radicals often have hydrogen bound to at least some of the carbon atoms of the organic radical. One example, of an organic radical that comprises no inorganic atoms is a 5, 6, 7,
8-tetrahydro-2-naphthyl radical. In some aspects, an organic radical can contain 1-10 inorganic heteroatoms bound thereto or therein, including halogens, oxygen, sulfur, nitrogen, phosphorus, and the like. Examples of organic radicals include but are not limited to an alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, mono-substituted amino, di-substituted amino, acyloxy, cyano, carboxy, carboalkoxy, alkylcarboxamide, substituted alkylcarboxamide, dialkylcarboxamide, substituted dialkylcarboxamide, alkylsulfonyl, alkylsulfmyl, thioalkyl, thiohaloalkyl, alkoxy, substituted alkoxy, haloalkyl, haloalkoxy, aryl, substituted aryl, heteroaryl, heterocyclic, or substituted heterocyclic radicals, wherein the terms are defined elsewhere herein. A few non-limiting examples of organic radicals that include heteroatoms include alkoxy radicals, trifluoromethoxy radicals, acetoxy radicals, dimethylamino radicals and the like.
[0046] As used herein, the terms "number average molecular weight" or "Mn" can be used interchangeably, and refer to the statistical average molecular weight of all the polymer chains in the sample and is defined by the formula:
where Mi is the molecular weight of a chain and Ni is the number of chains of that molecular weight. Mn can be determined for polymers, e.g., polycarbonate polymers, by methods well known to a person having ordinary skill in the art using molecular weight standards, e.g. polycarbonate standards or polystyrene standards, preferably certified or traceable molecular weight standards.
[0047] As used herein, the terms "weight average molecular weight" or "Mw" can be used interchangeably, and are defined by the formula:
Σ Ν,Μ,
where M; is the molecular weight of a chain and Ni is the number of chains of that molecular weight. Compared to Mn, Mw takes into account the molecular weight of a given chain in determining contributions to the molecular weight average. Thus, the greater the molecular weight of a given chain, the more the chain contributes to the Mw. Mw can be determined for polymers, e.g. polycarbonate polymers, by methods well known to a person having ordinary skill in the art using molecular weight standards, e.g. polycarbonate standards or polystyrene standards, preferably certified or traceable molecular weight standards.
[0048] As used herein, the terms "polydispersity index" or "PDI" can be used
interchangeably, and are defined by the formula:
Mn
The PDI has a value equal to or greater than 1 , but as the polymer chains approach uniform chain length, the PDI approaches unity.
[0049] The terms "BisA, " "BPA," or "bisphenol A," which can be used interchangeably, as used herein refers to a compound having a structure represented by the formula:
Figure imgf000011_0001
BisA can also be referred to by the name 4,4'-(propane-2,2-diyl)diphenol;
ρ,ρ'-isopropylidenebisphenol; or 2,2-bis(4-hydroxyphenyl)propane.. BisA has the CAS #
80-05-7.
[0050] As used herein, "polycarbonate" refers to an oligomer or polymer comprising residues of one or more dihydroxy compounds, e.g., dihydroxy aromatic compounds, joined by carbonate linkages; it also encompasses homopolycarbonates, copolycarbonates, and (co)polyester carbonates.
[0051] The terms "residues" and "structural units", used in reference to the constituents of the polymers, are synonymous throughout the specification.
[0052] Each of the materials disclosed herein are either commercially available and/or the methods for the production thereof are known to those of skill in the art.
[0053] It is understood that the compositions disclosed herein have certain functions. Disclosed herein are certain structural requirements for performing the disclosed functions, and it is understood that there are a variety of structures that can perform the same function that are related to the disclosed structures, and that these structures will typically achieve the same result.
COMPOSITION
[0054] As described above, the present disclosure describes polycarbonate blend compositions generally comprising a polycarbonate polymer, a first
polysiloxane -polycarbonate copolymer, a second polysiloxane-polycarbonate copolymer, and a colorant composition. The polycarbonate-siloxane blends achieve improved impact properties, as well as the ability to achieve deep black and bright white colors.
[0055] The present disclosure utilizes a first and a second polycarbonate-polysiloxane copolymer which offers good impact properties compared to standard polycarbonates, wherein the first polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 4 to 8 wt % diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer; and wherein the second polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 1 to 30 wt % diorganosiloxane based on the total weight of the second polysiloxane-polycarbonate copolymer. The second polysiloxane-polycarbonate copolymer is an opaque polycarbonate-polysiloxane copolymer which offers improved impact properties, but is unable to achieve the deep black colors due to the opacity of this copolymer. A blend of both polycarbonate-polysiloxane copolymers, along with a polycarbonate and a colorant composition, allows for improved impact properties while maintaining a constant formulation percentage of siloxane. Plus, the blend of both polycarbonate-polysiloxane copolymers, along with a polycarbonate and a colorant composition, allows for the ability to achieve deep black and bright white colors.
Specifically, the relative low color (YI <10 at 3.2 mm thickness) and high transparency (percent haze <3.0 at 3.2 mm thickness) give the blend the ability to achieve deep black and bright white colors.
[0056] The present disclosure describes a polycarbonate blend composition comprising: (a) a polycarbonate homopolymer; (b) a first polysiloxane-polycarbonate copolymer comprising: (i) poly diorganosiloxane blocks comprising repeating structural units of formula:
Figure imgf000013_0001
wherein the polydiorganosiloxane block length (E) is from 30 to 60; and (ii) polycarbonate blocks comprising polycarbonate units of formula:
Figure imgf000013_0002
wherein at least 60 percent of the total number of R1 groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the first polysiloxane -polycarbonate copolymer comprises a diorganosiloxane content of from 4 to 8 wt % diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer; (c) a second polysiloxane-polycarbonate copolymer comprising: (i) polydiorganosiloxane blocks comprising repeating structural units of formula:
Figure imgf000013_0003
wherein the polydiorganosiloxane block length (E) is from 30 to 100; and (ii) polycarbonate blocks comprising polycarbonate units of formula:
O
R— O C O wherein at least 60 percent of the total number of R1 groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the second polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 15 to 30 wt % diorganosiloxane based on the total weight of the second
polysiloxane-polycarbonate copolymer; and (d) a colorant composition; wherein the blend composition has an average melt flow rate (MFR) of 7 or greater measured at 300 °C/1.2 kg; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has a black color characterized by an average L* value of 27 or less as measured by the CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -30 °C of 650 J/m or greater and a % ductility of 100% according to ASTM D256-2010.
[0057] In one aspect, the invention relates to polycarbonate blend compositions comprising: (a) a first polysiloxane-polycarbonate copolymer comprising: i)
polydiorganosiloxane blocks comprising repeating structural units of formula:
Figure imgf000014_0001
wherein the polydiorganosiloxane block length (E) is from 30 to 60; and ii) polycarbonate blocks comprising polycarbonate units of formula:
Figure imgf000014_0002
wherein at least 60 percent of the total number of R1 groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the first polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 4 to 8 wt % diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer; (b) a second polysiloxane-polycarbonate copolymer comprising: i)
polydiorganosiloxane blocks comprising repeating structural units of formula:
Figure imgf000014_0003
wherein the polydiorganosiloxane block length (E) is from 30 to 100; and ii) polycarbonate blocks comprising polycarbonate units of formula:
O
R— O- c- o- wherein at least 60 percent of the total number of R1 groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the second polysiloxane -polycarbonate copolymer comprises a diorganosiloxane content of from 15 to 30 wt % diorganosiloxane based on the total weight of the second
polysiloxane -polycarbonate copolymer; and (c) a colorant composition; wherein the blend composition has an average melt flow rate (MFR) of 7 or greater measured at 300 °C/1.2 kg; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has a black color characterized by an average L* value of 28 or less as measured by the CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -30 °C of 600 J/m or greater and a % ductility of 80% according to ASTM D256-2010; and wherein R is the same or different, and is a C1-13 monovalent organic group; R2 is independently a divalent C1-C30 organic group; M is independently a halogen, cyano, nitro, Ci-C8 alkylthio, Ci-C8 alkyl, Ci-Cg alkoxy, C2-C8 alkenyl, C2-C8 alkenyloxy group, C3-C8 cycloalkyl, C3-C8 cycloalkoxy, C6-Cio aryl, C6-Cio aryloxy, C7-C12 aralkyl, C7- C12 aralkoxy, C7- C12 alkylaryl, or C7- C12 alkylaryloxy, wherein each n is independently 0, 1, 2, 3, or 4.
[0058] In one aspect, the invention relates to polycarbonate blend compositions comprising: (a) a polycarbonate polymer; (b) a first polysiloxane-polycarbonate copolymer comprising: i) polydiorganosiloxane blocks comprising repeating structural units of formula:
Figure imgf000015_0001
wherein the polydiorganosiloxane block length (E) is from 30 to 60; and ii) polycarbonate blocks comprising polycarbonate units of formula:
Figure imgf000015_0002
wherein at least 60 percent of the total number of R1 groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the first polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 4 to 8 wt % diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer; (c) a second polysiloxane-polycarbonate copolymer comprising: i)
polydiorganosiloxane blocks comprising repeating structural units of formula:
Figure imgf000016_0001
E
wherein the polydiorganosiloxane block length (E) is from 30 to 100; and ii) polycarbonate blocks comprising polycarbonate units of formula:
Figure imgf000016_0002
wherein at least 60 percent of the total number of R groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the second polysiloxane -polycarbonate copolymer comprises a diorganosiloxane content of from 15 to 30 wt % diorganosiloxane based on the total weight of the second
polysiloxane -polycarbonate copolymer; and (d) a colorant composition; wherein the blend composition has an average melt flow rate (MFR) of 7 or greater measured at 300°C/1.2 kg; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has a black color characterized by an average L* value of 28 or less as measured by the CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -30°C of 600 J/m or greater and a % ductility of 80% according to ASTM D256-2010; and wherein R is the same or different, and is a C1-13 monovalent organic group; R2 is independently a divalent C1-C30 organic group; M is independently a halogen, cyano, nitro, Ci-C8 alkylthio, Ci-C8 alkyl, Ci-Cg alkoxy, C2-C8 alkenyl, C2-C8 alkenyloxy group, C3-C8 cycloalkyl, C3-C8 cycloalkoxy, C6-Cio aryl, C6-Cio aryloxy, C7-C12 aralkyl, C7- C12 aralkoxy, C7- C12 alkylaryl, or C7- C12 alkylaryloxy, wherein each n is independently 0, 1, 2, 3, or 4.
[0059] In one aspect, each R2 is independently a divalent C1-C30 organic group such as a C1-C30 alkyl, C6-C30 aryl or C7-C30 alkylaryl.
[0060] Each M in the polydiorganosiloxane can be the same or different, and is a halogen, cyano, nitro, Ci-Cs alkylthio, Ci-Cg alkyl, Ci-Cg alkoxy, C2-C8 alkenyl, C2-C8 alkenyloxy group, C3-C8 cycloalkyl, C3-C8 cycloalkoxy, C6-Cio aryl, C6-Cio aryloxy, C7-C12 aralkyl, C7- C12 aralkoxy, C7- C12 alkylaryl, or C7- C12 alkylaryloxy, wherein each n is independently 0, 1, 2, 3, or 4.
[0061] In one aspect, M is bromo or chloro, an alkyl group such as methyl, ethyl, or propyl, an alkoxy group such as methoxy, ethoxy, or propoxy, or an aryl group such as phenyl, chlorophenyl, or tolyl, n= 0 to 4; R2 is a dimethylene, trimethylene or tetramethylene group; and R is a CI -8 alkyl, haloalkyl such as trifluoropropyl, cyanoalkyl, or aryl such as phenyl, chlorophenyl or tolyl. In another aspect, R is methyl, or a combination of methyl and trifluoropropyl, or a combination of methyl and phenyl. In still another aspect, M is methoxy, n is one, R2 is a divalent C1-C3 aliphatic group, and R is methyl.
POLYCARBONATE POLYMER
[0062] The polycarbonate polymer may be derived from one dihydroxy monomer or a combination of two or more dihydroxy aromatic monomers, respectively. To that end, as used herein the term "polycarbonate" and "polycarbonate resin" means compositions having repeating structural carbonate units of the formula (I):
O
— R'-O— 1— o— (I)
in which at least about 60 % of the total number of R1 groups are aromatic organic groups and the balance thereof are aliphatic, alicyclic, or aromatic groups. In one aspect, each R1 is an aromatic organic group, for example a group of the formula (II):
A1— Y1— A2 (II)
wherein each of A1 and A2 is a monocyclic divalent aryl group and Y1 is a bridging group having one or two atoms that separate A1 from A2. For example, one atom may separate A1 from A2, with illustrative examples of these groups including -0-, -S-, -S(O)-, -S(0)2-, -C(O)-, methylene, cyclohexyl-methylene, 2-[2.2.1]-bicycloheptylidene, ethylidene, isopropylidene, neopentylidene, cyclohexylidene, cyclopentadecylidene, cyclododecylidene, and
adamantylidene. The bridging group Y1 may be a hydrocarbon group or a saturated hydrocarbon group such as methylene, cyclohexylidene, or isopropylidene.
[0063] The polycarbonates may be produced from dihydroxy compounds having the formula HO-R^OH, wherein R1 is defined as above for formula (I). The formula
HO-R^OH includes bisphenol compounds of formula (III):
HO-A1— Y1— A2— OH (HI)
wherein Y1, A1 and A2 are as described above. Included are bisphenol compounds of general formula (IV):
Figure imgf000017_0001
wherein Ra and Rb each represent a halogen atom or a monovalent hydrocarbon group and may be the same or different; p and q are each independently integers of 0 to 4; and Xa represents one of the groups of formula (V):
Rc Re
I II
— C— or — C—
" d
R (V)
wherein Rc and Rd each independently represent a hydrogen atom or a monovalent linear alkyl or cyclic alkylene group and Re is a divalent hydrocarbon group. In one aspect, Rc and Rd represent a cyclic alkylene group; or a heteroatom-containing cyclic alkylene group comprising carbon atoms and heteroatoms with a valency of two or greater. In still a further aspect, a heteroatom-containing cyclic alkylene group comprises at least one heteroatom with a valency of 2 or greater, and at least two carbon atoms. Suitable heteroatoms for use in the heteroatom-containing cyclic alkylene group include -0-, -S-, and -N(Z)-, where Z is a substituent group selected from hydrogen, Ci_i2 alkyl, Ci_i2 alkoxy, or Ci_i2 acyl. Where present, the cyclic alkylene group or heteroatom-containing cyclic alkylene group may have 3 to 20 atoms, and may be a single saturated or unsaturated ring, or fused polycyclic ring system wherein the fused rings are saturated, unsaturated, or aromatic.
[0064] Other useful dihydroxy compounds having the formula HO-R^OH include aromatic dihydroxy compounds of formula (VII):
Figure imgf000018_0001
wherein each Rh is independently a halogen atom, a Cno hydrocarbyl such as a Ci_io alkyl group, a halogen substituted Ci_io hydrocarbyl such as a halogen-substituted Ci_io alkyl group, and n is 0 to 4. The halogen is usually bromine, though it is not limited to only bromine.
[0065] Some exemplary dihydroxy compounds include: 4,4'-dihydroxybiphenyl, 1 ,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)- 1 -naphthylmethane,
1 ,2-bis(4-hydroxyphenyl)ethane, 1 , 1 -bis(4-hydroxyphenyl)- 1 -phenylethane,
2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 1 , 1 -bis (hydroxyphenyl)cyclopentane,
1 , 1 -bis(4-hydroxyphenyl)cyclohexane, 1 , 1 -bis(4-hydroxyphenyl)isobutene,
1 , 1 -bis(4-hydroxyphenyl)cyclododecane, trans-2,3-bis(4-hydroxyphenyl)-2-butene,
2,2-bis(4-hydroxyphenyl)adamantine, alpha, alpha' -bis(4-hydroxyphenyl)toluene,
bis(4-hydroxyphenyl)acetonitrile, 2,2-bis(3-methyl-4-hydroxyphenyl)propane,
2,2-bis(3-ethyl-4-hydroxyphenyl)propane, 2,2-bis(3-n-propyl-4-hydroxyphenyl)propane, 2,2-bis(3-isopropyl-4-hydroxyphenyl)propane, 2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 2,2-bis(3-methoxy-4-hydroxyphenyl)propane,
2.2- bis(4-hydroxyphenyl)hexafluoropropane, 1 , 1 -dichloro-2,2-bis(4-hydroxyphenyl)ethylene, 1 , 1 -dibromo-2,2-bis(4-hydroxyphenyl)ethylene,
1 , 1 -dichloro-2,2-bis(5-phenoxy-4-hydroxyphenyl)ethylene, 4,4'-dihydroxybenzophenone,
3.3- bis(4-hydroxyphenyl)-2-butanone, l,6-bis(4-hydroxyphenyl)-l,6-hexanedione, ethylene glycol bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfone,
9,9-bis(4-hydroxyphenyl)fluorine, 2,7-dihydroxypyrene, 6,6'-dihydroxy-3,3,3',3'- tetramethylspiro(bis)indane ("spirobiindane bisphenol"), 3,3-bis(4-hydroxyphenyl)phthalide,
2.6- dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene, 2,7-dihydroxyphenoxathin,
2.7- dihydroxy-9, 10-dimethylphenazine, 3 ,6-dihydroxydibenzofuran,
3,6-dihydroxydibenzothiophene, and 2,7-dihydroxycarbazole, resorcinol, substituted resorcinol compounds such as 5 -methyl resorcinol, 5 -ethyl resorcinol, 5 -propyl resorcinol, 5 -butyl resorcinol, 5-t-butyl resorcinol, 5 -phenyl resorcinol, 5-cumyl resorcinol,
2,4,5, 6-tetrafluoro resorcinol, 2,4,5, 6-tetrabromo resorcinol, or the like; catechol;
hydroquinone; substituted hydroquinones such as 2-methyl hydroquinone, 2-ethyl
hydroquinone, 2-propyl hydroquinone, 2-butyl hydroquinone, 2-t-butyl hydroquinone, 2-phenyl hydroquinone, 2-cumyl hydroquinone, 2,3,5,6-tetramethyl hydroquinone,
2,3,5,6-tetra-t-butyl hydroquinone, 2, 3, 5, 6-tetrafluoro hydroquinone, 2, 3, 5, 6-tetrabromo hydroquinone, and the like, as well as combinations comprising at least one of the foregoing dihydroxy compounds.
[0066] Specific examples of bisphenol compounds that may be represented by formula (3) include l,l-bis(4-hydroxyphenyl) methane, l,l-bis(4-hydroxyphenyl) ethane,
2,2-bis(4-hydroxyphenyl) propane (hereinafter "bisphenol A" or "BP A"),
2,2-bis(4-hydroxyphenyl) butane, 2,2-bis(4-hydroxyphenyl) octane, l,l-bis(4-hydroxyphenyl) propane, l,l-bis(4-hydroxyphenyl) n-butane, 2,2-bis(4-hydroxy-l-methylphenyl) propane, l,l-bis(4-hydroxy-t-butylphenyl) propane, and
1 , 1 -bis(4-hydroxy-3 -methylphenyl)cyclohexane (DMBPC) . Combinations comprising at least one of the foregoing dihydroxy compounds may also be used.
[0067] In yet a further aspect, polycarbonates with branching groups can be useful, provided that such branching does not significantly adversely affect desired properties of the polycarbonate. Branched polycarbonate blocks can be prepared by adding a branching agent during polymerization. These branching agents include poly functional organic compounds containing at least three functional groups selected from hydroxyl, carboxyl, carboxylic anhydride, haloformyl, and mixtures of the foregoing functional groups. Specific examples include trimellitic acid, trimellitic anhydride, trimellitic trichloride, tris-p-hydroxy phenyl ethane, isatin-bis-phenol, tris-phenol TC (l,3,5-tris((p-hydroxyphenyl)isopropyl)benzene), tris-phenol PA (4-(4'-(l,l-bis(p-hydroxyphenyl)-ethyl) alpha, alpha-dimethylbenzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid, and benzophenone tetracarboxylic acid. In one aspect, a branching agent can be added at a level of about 0.05 to about 2.0 wt %. In still another aspect, mixtures comprising linear polycarbonates and branched polycarbonates can be used.
[0068] In at least one aspect, the composition may include, as the polycarbonate polymer, at least one bisphenol-A polycarbonate polymer. Non-limiting examples of the
polycarbonate may include high and low flow Lexan™ polycarbonate polymers available in various grades from SABIC Innovative Plastics.
[0069] In one aspect, the polycarbonate may be present in the composition as a total amount ranging from 5 wt % to 60 wt %. In another aspect, the polycarbonate may be present in the composition as a total amount ranging from 10 wt % to 55 wt %. In a further aspect, the polycarbonate may be present in the composition as a total amount ranging from 10 wt % to 50 wt %. In an even further aspect, the polycarbonate may be present in the composition as a total amount ranging from 15 wt% to 45 wt %. The polycarbonate may be present as a single bisphenol-A polycarbonate or as a mixture of two or more bisphenol-A polycarbonates.
[0070] In another aspect, one polycarbonate may be present in the composition in an amount ranging from 1 wt % to 60 wt %. In a further aspect, one polycarbonate may be present in an amount ranging from 3 wt % to 55 wt %. In another aspect, one polycarbonate may be present in an amount ranging from 3 wt % to 50 wt %. In a still further aspect, one polycarbonate may be present in an amount ranging from 5 wt % to 45 wt %. In a yet further aspect, the polycarbonate polymer is present in an amount in the range of from 15 wt% to 30 wt% relative to the total weight percent of the polycarbonate polymer, first
polysiloxane -polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer. In an even further aspect, the polycarbonate polymer is present in an amount in the range of from 22 wt% to 29 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer. [0071] In a further aspect, the polycarbonate polymer is present in an amount in the range of from 15 wt% to 45 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer. In a still further aspect, the polycarbonate polymer is present in an amount in the range of from 24 wt% to 45 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second
polysiloxane-polycarbonate copolymer. In a yet further aspect, the polycarbonate polymer is present in an amount in the range of from 0 wt% to 55 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer. In an even further aspect, the polycarbonate polymer is present in an amount in the range of from 0 wt% to 45 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
[0072] In at least one aspect, the bisphenol-A polycarbonate has a weight-averaged molecular weight, Mw, between 18,000 and 32,000 g/mol. In a further aspect, the
Bisphenol-A polycarbonate has a weight-averaged molecular weight, Mw, between 28,000 and 32,000 g/mol. In at least one aspect, the weight-average molecular weight may be measured using GPC. In at least one aspect, the weight-average molecular weight may be measured using standard procedures, for example, using the method of ASTM D1003.
[0073] In various aspects, the polycarbonate polymer comprises a first polycarbonate polymer and a second polycarbonate polymer. In a further aspect, the first polycarbonate polymer is a low flow polycarbonate. In a still further aspect, the second polycarbonate polymer is a high flow polycarbonate.
[0074] In a further aspect, the first polycarbonate polymer is present in an amount in the range of from 11 wt% to 29 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second
polysiloxane-polycarbonate copolymer and wherein the second polycarbonate polymer is present in an amount in the range of from greater than 0 wt% to 8 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer. In a still further aspect, the first polycarbonate polymer is present in an amount in the range of from 14 wt% to 29 wt% relative to the total weight percent of the polycarbonate polymer, first
polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer and wherein the second polycarbonate polymer is present in an amount in the range of from greater than 0 wt% to 8 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane -polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
[0075] In a further aspect, the first polycarbonate polymer is present in an amount in the range of from 10 wt% to 30 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second
polysiloxane-polycarbonate copolymer and wherein the second polycarbonate polymer is present in an amount in the range of from greater than 0 wt% to 15 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
POLYSILOXANE-POLYCARBONATE COPOLYMER
[0076] The polysiloxane-polycarbonate copolymer has a polysiloxane structural unit and a polycarbonate structural unit. The polycarbonate structural unit of the
polysiloxane-polycarbonate copolymer may be derived from carbonate units of formula (I) as described above. The carbonate units may be derived from one or more dihydroxy monomers of formula (III) including bisphenol compound of formula (IV), both as described and incorporated herein from above. The dihydroxy compound may be bisphenol-A.
[0077] In one aspect, R is the same or different, and is a Ci_i3 monovalent organic group. For example, R can be a C1-C13 alkyl group, Ci- C13 alkoxy group, C2- C13 alkenyl group, C2- Ci3 alkenyloxy group, C3-C6 cycloalkyl group, C3-C6 cycloalkoxy group, C6-Ci4 aryl group, C6-Cio aryloxy group, C7- C13 aralkyl group, C7- C13 aralkoxy group, C7- C13 alkylaryl group, or C7- Ci3 alkylaryloxy group. The foregoing groups can be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof. In an aspect, where a transparent polymer is desired, R does not contain any halogen. Combinations of the foregoing R groups can be used in the same polymer.
[0078] The polysiloxane structural unit may be derived from a siloxane-containing dihydroxy compounds (also referred to herein as "hydroxyaryl end-capped polysiloxanes") that contain diorganosiloxane unit blocks of formula (IX):
Figure imgf000022_0001
wherein each occurrence of R is same or different, and is a C1-13 monovalent organic group. For example, R can be a C1-C13 alkyl group, Ci- C13 alkoxy group, C2- C13 alkenyl group, C2- Ci3 alkenyloxy group, C3-C6 cycloalkyl group, C3-C6 cycloalkoxy group, C6-Ci4 aryl group, C6-Cio aryloxy group, C7- C13 aralkyl group, C7- C13 aralkoxy group, C7- C13 alkylaryl group, or C7- Ci3 alkylaryloxy group. The foregoing groups can be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof. In an aspect, where a transparent polycarbonate is desired, R does not contain any halogen. Combinations of the foregoing R groups can be used in the same polycarbonate.
[0079] The value of E in formula (IX) can vary widely depending on the type and relative amount of each of the different units in the polycarbonate, the desired properties of the polycarbonate, and like considerations. Generally, E can have an average value of about 2 to about 1 ,000, specifically about 2 to about 500, more specifically about 2 to about 100. In an aspect, E has an average value of about 4 to about 90, specifically about 5 to about 80, and more specifically about 40 to about 60.
[0080] In one aspect, the polysiloxane blocks are provided by repeating structural units of formula (X):
Figure imgf000023_0001
wherein E is as defined above; each R is the same or different, and is as defined above; and each Ar is the same or different, and Ar is one or more C6-C30 aromatic group(s), or one or more alkyl containing C6-C30 aromatic group(s), wherein the bonds are directly connected to an aromatic moiety. The — O— Ar— O— groups in formula (X) can be, for example, a C6-C30 dihydroxyaromatic compound. Combinations comprising at least one of the foregoing dihydroxyaromatic compounds can also be used. Exemplary dihydroxyaromatic compounds are l ,l-bis(4-hydroxyphenyl) methane, l ,l-bis(4-hydroxyphenyl)ethane,
2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane,
2,2-bis(4-hydroxyphenyl)octane, 1 , 1 -bis(4-hydroxyphenyl)propane,
1 , 1 -bis(4-hydroxyphenyl)n-butane, 2,2-bis(4-hydroxy- 1 -methylphenyl)propane,
1 , 1 -bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl sulfide),
1 , 1 -bis(4-hydroxy-3-methylphenyl)cyclohexane, and
l , l-bis(4-hydroxy-t-butylphenyl)propane, or a combination comprising at least one of the foregoing dihydroxy compounds.
[0081] Polycarbonates comprising such units can be derived from the corresponding dihydroxy compound of formula (XI):
Figure imgf000024_0001
(XI)
wherein Ar and E are as described above. Compounds of formula (XI) can be obtained by the reaction of a dihydroxyaromatic compound with, for example, an alpha,
omega-bis-acetoxy-polydiorganosiloxane oligomer under phase transfer conditions.
Compounds of formula (XI) can also be obtained from the condensation product of a dihydroxyaromatic compound, with, for example, an alpha, omega
bis-chloro-polydimethylsiloxane oligomer in the presence of an acid scavenger.
[0082] In another aspect, polydiorganosiloxane blocks can comprise units of formula (XII):
-o- -Rfi sioHsi- Re -O-
R R
(XII)
wherein R and E are as described above, and each 5 is independently a divalent C1-C30 organic group such as a C1-C30 alkyl, C6-C30 aryl or C7-C30 alkylaryl. The polysiloxane blocks corresponding to formula (XII) are derived from the corresponding dihydroxy compound of formula (XIII):
Figure imgf000024_0002
wherein R and E and R6 are as described for formula (XII) above.
[0083] In another aspect, the polydiorganosiloxane blocks are provided by repeating structural units of formula (XIV):
Figure imgf000024_0003
wherein R and E are as defined above. R7 in formula (XIV) is a divalent C2-C8 aliphatic group. Each M in formula (XIV) can be the same or different, and is a halogen, cyano, nitro, Ci-Cg alkylthio, Ci-Cg alkyl, Ci-Cg alkoxy, C2-Cg alkenyl, C2-Cg alkenyloxy group, C3-Cg cycloalkyl, C3-Cg cycloalkoxy, C6-Cio aryl, C6-Cio aryloxy, C7-Ci2 aralkyl, C7- Ci2 aralkoxy, C7- C12 alkylaryl, or C7- C12 alkylaryloxy, wherein each n is independently 0, 1, 2, 3, or 4.
[0084] In one aspect, M of formula (XIV) is bromo or chloro, an alkyl group such as methyl, ethyl, or propyl, an alkoxy group such as methoxy, ethoxy, or propoxy, or an aryl group such as phenyl, chlorophenyl, or tolyl, n= 0 to 4; R7 is a dimethylene, trimethylene or tetramethylene group; and R is a Ci_g alkyl, haloalkyl such as trifluoropropyl, cyanoalkyl, or aryl such as phenyl, chlorophenyl or tolyl. In another aspect, R is methyl, or a combination of methyl and trifluoropropyl, or a combination of methyl and phenyl. In still another aspect, M is methoxy, n is one, R7 is a divalent Ci-C3 aliphatic group, and R is methyl.
[0085] Polysiloxane-polycarbonates comprising units of formula (XIV) can be derived from the corresponding dihydroxy polydiorganosiloxane of formula (XV):
Figure imgf000025_0001
(XV) wherein each of R, E, M, R7, and n are as described above. Such dihydroxy polysiloxanes can be made by effecting a platinum-catalyzed addition between a siloxane hydride of formula (XVI):
Figure imgf000025_0002
wherein R and E are as previously defined, and an aliphatically unsaturated monohydric phenol. Exemplary aliphatically unsaturated monohydric phenols included, for example, eugenol, 2-allylphenol, 4-allyl-2-methylphenol, 4-allyl-2-phenylphenol,
4-allyl-2-bromophenol, 4-allyl-2-t-butoxyphenol, 4-phenyl-2-phenylphenol,
2-methyl-4-propylphenol, 2-allyl-4,6-dimethylphenol, 2-allyl-4-bromo-6-methylphenol, 2-allyl-6-methoxy-4-methylphenol, 4-allylphenol, and 2-allyl-4,6-dimethylphenol.
Combinations comprising at least one of the foregoing can also be used.
[0086] In still a further aspect, the polysiloxane polycarbonate copolymer can be a block copolymer of polycarbonate and eugenol capped polydimethylsilioxane (PDMS) having the general structure (XVII) as shown below:
Figure imgf000026_0001
(XVII),
wherein the polysiloxane -polycarbonate block copolymer comprises polycarbonate blocks derived from Bisphenol-A and diorganopolysiloxane blocks of the general formula (XVIII):
Figure imgf000026_0002
(XVIII).
[0087] According to exemplary aspects, the polysiloxane block length "X" of formula (XVIII) is from about 40 to about 60. As describe above, the polysiloxane-polycarbonate block copolymer can optionally be end-capped with p-cumyl-phenol.
[0088] Diorganopolysiloxane blocks of formula (XVIII) can be derived from the corresponding dihydroxy compound of formula (XIX):
Figure imgf000026_0003
wherein x is as described above. Compounds of this type and others are further described in U.S. Patent 4,746,701 to Kress, et al and US 8,017,0697 to Carrillo. Compounds of this formula can, for example, be obtained by the reaction of the appropriate dihydroxyarylene compound with, for example, an alpha, omega-bisacetoxypolydiorangonosiloxane under phase transfer conditions.
[0089] The polycarbonate -polysiloxane copolymer may be manufactured by reaction of a dihydroxy polysiloxane with a carbonate source and a dihydroxy aromatic compound such as bisphenol-A, optionally in the presence of a phase transfer catalyst as described above.
Suitable conditions are similar to those useful in forming polycarbonates as described above. For example, the copolymers are prepared by phosgenation, at temperatures from below 0 °C to about 100 °C, preferably about 25 °C to about 50 °C. Since the reaction is exothermic, the rate of phosgene addition may be used to control the reaction temperature. The amount of phosgene required will generally depend upon the amount of the dihydric reactants.
Alternatively, the polycarbonate-polysiloxane copolymers may be prepared by co-reacting in a molten state, the dihydroxy monomers and a diaryl carbonate ester, such as diphenyl carbonate, in the presence of a transesterification catalyst as described above.
[0090] In the production of the polycarbonate-polysiloxane copolymer, the amount of dihydroxy diorganopolysiloxane is selected so as to provide the desired amount of
diorganopolysiloxane units in the copolymer. The particular amounts used will therefore be determined depending on desired physical properties of the composition, the value of x (within the range of about 40 to about 60), and the type and relative amount of each component in the composition, including the type and amount of polycarbonate, type and amount of impact modifier, type and amount of polycarbonate-polysiloxane copolymer, and type and amount of any other additives. Suitable amounts of dihydroxy
diorganopolysiloxane can be determined by one of ordinary skill in the art without undue experimentation using the guidelines taught herein. For example, the amount of dihydroxy polydiorganosiloxane may be selected so as to produce a copolymer comprising about 20 wt.% polydimethylsiloxane. In one aspect, the copolymer may comprise about 20 wt.% siloxane.
[0091] In one aspect, the polysiloxane units are of formula (9)
Figure imgf000027_0001
wherein each R is independently a Ci_i3 monovalent hydrocarbyl group. For example, each R can independently be a Ci_i3 alkyl group, Ci_i3 alkoxy group, C2-13 alkenyl group, C2-13 alkenyloxy group, C3_6 cycloalkyl group, C3_6 cycloalkoxy group, C6-14 aryl group, C6-io aryloxy group, C7-13 arylalkyl group, C7-13 arylalkoxy group, C7-13 alkylaryl group, or C7-13 alkylaryloxy group. The foregoing groups can be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof. In an aspect no halogens are present. Combinations of the foregoing R groups can be used in the same copolymer. In an aspect, the polysiloxane comprises R groups that have minimal hydrocarbon content. In a specific aspect, an R group with a minimal hydrocarbon content is a methyl group.
[0092] In one aspect, the average value of E in formula (9) can vary widely depending on the type and relative amount of each component in the thermoplastic composition, whether the polymer is linear, branched or a graft copolymer, the desired properties of the composition, and like considerations. In an aspect, E has an average value of 2 to 500, 2 to 200, or 5 to 100, 10 to 100, or 10 to 80. In an aspect E has an average value of 16 to 50, more specifically 20 to 45, and even more specifically 25 to 45. In another aspect, E has an average value of 4 to 50, 4 to 15, specifically 5 to 15, more specifically 6 to 15, and still more specifically 7 to 10.
[0093] In an aspect, the pol siloxane units are structural units of formula (9a)
Figure imgf000028_0001
wherein E is as defined above; each R can independently be the same or different, and is as defined above; and each Ar can independently be the same or different, and is a substituted or unsubstituted C6-3o compound containing an aromatic group, wherein the bonds are directly connected to the aromatic moiety. The Ar groups in formula (9a) can be derived from a C6_3o dihydroxy aromatic compound, for example a bisphenol compound as described above or a monoaryl dihydroxy compound (6) above. Combinations comprising at least one of the foregoing dihydroxy aromatic compounds can also be used. Exemplary dihydroxy aromatic compounds are resorcinol (i.e., 1,3-dihydroxybenzene), 4-methyl-l,3-dihydroxybenzene, 5-methyl- 1 ,3-dihydroxybenzene, 4,6-dimethyl- 1 ,3-dihydroxybenzene, 1 ,4-dihydroxybenzene,
1.1- bis(4-hydroxyphenyl) methane, l,l-bis(4-hydroxyphenyl) ethane,
2.2- bis(4-hydroxyphenyl) propane, 2,2-bis(4-hydroxyphenyl) butane,
2,2-bis(4-hydroxyphenyl) octane, l,l-bis(4-hydroxyphenyl) propane,
l,l-bis(4-hydroxyphenyl) n-butane, 2,2-bis(4-hydroxy-l-methylphenyl) propane,
l,l-bis(4-hydroxyphenyl) cyclohexane, bis(4-hydroxyphenyl sulfide), and
l,l-bis(4-hydroxy-t-butylphenyl) propane. Combinations comprising at least one of the foregoing dihydroxy compounds can also be used. In an aspect, the dihydroxy aromatic compound is unsubstituted, or is does not contain non-aromatic hydrocarbyl substituents such as alkyl, alkoxy, or alkylene substituents.
[0094] In a specific aspect, where Ar is derived from resorcinol, the polysiloxane units are of the formula(9a-l)
Figure imgf000028_0002
or, where Ar is derived from bisphenol- A, the polysiloxane has the formula (9a-2)
Figure imgf000029_0001
or a combination comprising at least one of the foregoing can be used, wherein E has an average value as described above, specifically an average value of 2 to 200. In at least one aspect, the first polysiloxance-polycarbonate has an average haze of less than 2.5 %.
[0095] In one aspect, the first polysiloxane-polycarbonate, the polydiorganosiloxane block length (E) is from 30 to 60. In one aspect, E is from 40 to 60, from 30 to 50, from 50 to 60, from 40 to 50, or from 30 to 40.
[0096] In one aspect, each R2 is independently a divalent Ci-C30 organic group such as a Ci-C3o alkyl, C6-C3o aryl or C7-C3o alkylaryl.
[0097] The first polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 4 to 8 wt % diorganosiloxane based on the total weight of the first
polysiloxane-polycarbonate copolymer. For example, the first polysiloxane-polycarbonate copolymer may comprise a diorganosiloxane content of from 4 to 7 wt %, or from 5 to 7 wt% diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer. In one aspect, the first polysiloxane-polycarbonate copolymer may comprise a
diorganosiloxane content of about 6 wt % diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer.
[0098] In one aspect, the second polysiloxane-polycarbonate the polydiorganosiloxane block length (E) is from 30 to 100. In one aspect, E is from 40 to 90, from 50 to 80, from 60 to 70, from 30 to 50, from 50 to 100, or from 50 to 70.
[0099] The second polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 15 to 30 wt % diorganosiloxane based on the total weight of the second polysiloxane-polycarbonate copolymer. For example, the second
polysiloxane-polycarbonate copolymer may comprise a diorganosiloxane content of from 15 to 25 wt %, from 17 to 23 wt %, or from 19 to 21 wt % diorganosiloxane based on the total weight of the second polysiloxane-polycarbonate copolymer. In one aspect, the second polysiloxane-polycarbonate copolymer may comprise a diorganosiloxane content of about 20 wt % diorganosiloxane based on the total weight of the second polysiloxane-polycarbonate copolymer
[00100] In at least one aspect, the first polysiloxane-polycarbonate copolymer has an weight-averaged molecular weight, Mw, between 20,000 and 25,000 g/mol and injection molded parts from the blend composition have an average haze of less than 2.5 % at a thickness of 3.2 mm, using the method of ASTM D1003. In a further aspect, the weight-averaged molecular weight, Mw, ranges from 21,000 to 24,000 g/mol, for example ranging from 22,000 to 24,000 g/mol. In at least one aspect, the weight-average molecular weight may be measured using Gel Permeation Chromatography (GPC) using polycarbonate standards. Alternatively, molecular weight determinations can be performed using gel permeation chromatography (GPC), using a crosslinked styrene-divinylbenzene column and calibrated to polycarbonate references. In various aspects, samples are prepared at a concentration of about 1 mg/ml, and are eluted at a flow rate of about 1.0 ml/min.
[00101] In a further aspect, the first polysiloxane-polycarbonate copolymer has an weight-averaged molecular weight, Mw, in the range of from 20,000 to 25,000 and wherein an injection molded part having a thickness of 3.2 mm formed from the blend composition has an average haze of less than 2.5 % measured according to ASTM D1003.
[00102] In at least one aspect, the first polysiloxane-polycarbonate copolymer has a
PolyDispersitylndex (PDI) ranging from 2 to 5, for example ranging from 2 to 4, or from 2 to
3. In another aspect, the second polysiloxane-polycarbonate copolymer has a
PolyDispersitylndex (PDI) ranging from 2 to 5, for example ranging from 2 to 4, or from 2 to ">
[00103] In a further aspect, the second polysiloxane-polycarbonate copolymer has a weight-averaged molecular weight, Mw, between 25,000 and 35,000 g/mol. In another aspect, the weight-averaged molecular weight, Mw, ranges from 27,000 to 33,000 g/mol, for example, ranging from 28,000 to 32,000 g/mol, further for example, 29,000 to 31,000 g/mol. In at least one aspect, the weight-average molecular weight may be measured using Gel Permeation Chromatography (GPC) using polycarbonate standards. In at least one aspect, the weight-average molecular weight may be measured using standard procedures, for example, using the method of ASTM D1003.
[00104] In at least one aspect, the composition may comprise at least one
polysiloxane-polycarbonate copolymer. Non-limiting examples of
polysiloxane-polycarbonate copolymers which may be used include a transparent polysiloxane-polycarbonate copolymer with a Mw of 23,000 g/mol, 6.0% siloxane, percent haze less than 2.5, or an opaque polysiloxane-polycarbonate copolymer with a Mw of 30,000 g/mol, 20.0% siloxane. In a further aspect, the second polysiloxane-polycarbonate copolymer is an opaque resin.
[00105] In at least one aspect, the siloxane units of the first and second
polysiloxane-polycarbonate copolymer are dimethyl siloxane units. [00106] In a further aspect, the polydiorganosiloxane has moieties derived from eugenol, 4-allylphenol, or 2-allylphenol
[00107] In one aspect, the composition may comprise a total amount of polycarbonate copolymer ranging from 50 wt % to 95 wt %. In another aspect, the composition may comprise a total amount of polycarbonate copolymer ranging from 60 wt % to 90 wt %. In a further aspect, the composition may comprise a total amount of polysiloxane-polycarbonate copolymer ranging from 65 wt % to 90 wt %. In one aspect, the composition may comprise a total amount of polysiloxane-polycarbonate copolymer ranging from 70 wt % to 85 wt %. The polysiloxane-polycarbonate copolymer may be present as a single
polysiloxane-polycarbonate or as a mixture of two or more polysiloxane -polycarbonates.
[00108] In one aspect, at least one polysiloxane-polycarbonate copolymer may be present in an amount ranging from 1 wt % to 95 wt%. In a further aspect, at least one
polysiloxane-polycarbonate copolymer may be present in an amount ranging from 2 wt % to 90 wt %. In another aspect, at least one polysiloxane-polycarbonate copolymer may be present in an amount ranging from 2 wt % to 85 wt %. In one aspect, the second polysiloxane-polycarbonate copolymer has at least 5 wt %. In another aspect, the second polysiloxane-polycarbonate copolymer ranges from 5 wt % to 95 wt %.
[00109] In one aspect, the second polysiloxane-polycarbonate copolymer is present in the blend composition in an amount less than 5 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second
polysiloxane-polycarbonate copolymer.
[00110] In one aspect, the second polysiloxane-polycarbonate copolymer is present in the blend composition in an amount of about 2.5 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second
polysiloxane-polycarbonate copolymer. In a further aspect, the second
polysiloxane-polycarbonate copolymer is present in the blend composition in an amount of about 4 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer. In a still further aspect, the second polysiloxane-polycarbonate copolymer is present in the blend composition in an amount less than 5 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second
polysiloxane-polycarbonate copolymer.
[00111] In one aspect, combining the first polysiloxane-polycarbonate and the second polysiloxane-polycarbonate, the total weight percentage of siloxane ranges from 4.5 wt % to 5.5 wt % based on the total combined weight of the first polysiloxane-polycarbonate, second polysiloxane-polycarbonate, and polycarbonate. For example, the total weight percentage of siloxane ranges from 4.5 wt % to 5.3 wt % based on the total combined weight of the first polysiloxane-polycarbonate, second polysiloxane-polycarbonate, and polycarbonate.
Further for example, the total weight percentage of siloxane ranges from 4.5 wt % to 5.0 wt % based on the total combined weight of the first polysiloxane-polycarbonate, second
polysiloxane-polycarbonate, and polycarbonate. Yet further for example, the total weight percentage of siloxane ranges from 4.6 wt % to 4.9 wt % based on the total combined weight of the first polysiloxane-polycarbonate, second polysiloxane-polycarbonate, and
polycarbonate. In one aspect, the total weight percentage of siloxane is 4.98 wt % based on the total combined weight of the first polysiloxane-polycarbonate, second
polysiloxane-polycarbonate, and polycarbonate.
[00112] In a further aspect, the total weight percentage of siloxane ranges from 4.0 wt % to 6.6 wt % based on the total combined weight of the first polysiloxane-polycarbonate, second polysiloxane-polycarbonate, and the polycarbonate. In a still further aspect, the total weight percentage of siloxane ranges from 4.0 wt % to 7 wt % based on the total combined weight of the first polysiloxane-polycarbonate, second polysiloxane-polycarbonate, and the polycarbonate.
[00113] In various further aspects, the total combined weight percent of the first and second polysiloxane-polycarbonate copolymers present in the blend composition is in the range of from 70 wt% to 80 wt% relative to the total combined weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second
polysiloxane-polycarbonate copolymer. In a further aspect, the total combined weight percent of the first and second polysiloxane-polycarbonate copolymers present in the blend composition is in the range of from 54 wt% to 100 wt% relative to the total combined weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer. In a still further aspect, the first polysiloxane-polycarbonate copolymer is present in an amount in the range of from 50 wt% to 95 wt% relative to the total combined weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
[00114] In a further aspect, the first polysiloxane-polycarbonate copolymer is present in an amount in the range of from 65 wt% to 75 wt% relative to the total combined weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer. In a still further aspect, the second polysiloxane -polycarbonate copolymer is present in an amount in the range of from greater than 0 wt% to 5 wt% relative to the total combined weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second
polysiloxane-polycarbonate copolymer.
[00115] In various aspects, the total combined weight percent of the first and second polysiloxane-polycarbonate copolymers present in the blend composition is in the range of from 50 wt% to 90 wt% relative to the total combined weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second
polysiloxane-polycarbonate copolymer.
[00116] In a further aspect, the first polysiloxane-polycarbonate copolymer is present in an amount in the range of from 50 wt% to 85 wt% relative to the total combined weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer. In a still further aspect, the second
polysiloxane-polycarbonate copolymer is present in an amount in the range of from greater than 0 wt% to 5 wt% relative to the total combined weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second
polysiloxane-polycarbonate copolymer.
COLORANT COMPOSITION
[00117] The disclosed composition comprises a colorant composition. The colorant composition comprises primarily organic colorants. As such, the composition comprises less than 1.5 wt % of an inorganic colorant based on the total colorant composition. In another aspect, the composition comprises an inorganic colorant based on the total weight of the composition ranging from 0.25 wt % to 1.5 wt %. In one aspect, the inorganic colorant is carbon black. As such, the composition comprises carbon black in an amount less than 1.5 wt % of the total colorant composition.
[00118] In a further aspect, the colorant composition comprises less than 12 wt % of an inorganic colorant based on the total weight of the colorant composition. In a still further aspect, the colorant composition comprises less than 10 wt % of an inorganic colorant based on the total weight of the colorant composition. In a yet further aspect, the colorant composition comprises less than 8 wt % of an inorganic colorant based on the total weight of the colorant composition. In an even further aspect, the colorant composition comprises less than 6 wt % of an inorganic colorant based on the total weight of the colorant composition. In a still further aspect, the colorant composition comprises less than 5 wt % of an inorganic colorant based on the total weight of the colorant composition. OPTIONAL POLYMER ADDITIVES
[00119] In addition to the foregoing components, the disclosed polycarbonate blend compositions can optionally comprise a balance amount of one or more additive materials ordinarily incorporated in polycarbonate resin compositions of this type, with the proviso that the additives are selected so as to not significantly adversely affect the desired properties of the polycarbonate composition. Combinations of additives can be used. Such additives can be mixed at a suitable time during the mixing of the components for forming the composition. Exemplary and non-limiting examples of additive materials that can be present in the disclosed polycarbonate compositions include an acid scavenger, anti-drip agent, antioxidant, antistatic agent, chain extender, colorant (e.g., pigment and/or dye), de-molding agent, flow promoter, lubricant, mold release agent, plasticizer, quenching agent, stabilizer (including for example a thermal stabilizer, a hydrolytic stabilizer, or a light stabilizer), UV absorbing additive, and UV reflecting additive, or any combination thereof.
[00120] For example, the disclosed composition can comprise one or more fillers, acids, specialty chemicals stabilizers, flame-retardants, impact modifiers, colorant, and/or mold release agents. Further for example, the disclosed composition can comprise Irgaphos 168 Ciba Specialty Chemicals and pigments. The disclosed composition may also comprise dilute phosphorous acid, for example 100 times dilution.
[00121] In a further aspect, the disclosed polycarbonate blend compositions can further comprise a primary antioxidant or "stabilizer" (e.g., a hindered phenol) and, optionally, a secondary antioxidant (e.g., a phosphate and/or thioester). Suitable antioxidant additives include, for example, organic phosphites such as tris(nonyl phenyl)phosphite,
tris(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite or the like; alkylated monophenols or polyphenols;
alkylated reaction products of polyphenols with dienes, such as
tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane, or the like;
butylated reaction products of para-cresol or dicyclopentadiene; alkylated hydroquinones; hydroxylated thiodiphenyl ethers; alkylidene-bisphenols; benzyl compounds; esters of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid with monohydric or polyhydric alcohols; esters of beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydric or polyhydric alcohols; esters of thioalkyl or thioaryl compounds such as distearylthiopropionate, dilaurylthiopropionate, ditridecylthiodipropionate,
octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,
pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate or the like; amides of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid or the like, or combinations comprising at least one of the foregoing antioxidants.
[00122] In a further aspect, the antioxidant is a primary antioxidant, a secondary antioxidant, or combinations thereof. In a still further aspect, the primary antioxidant is selected from a hindered phenol and secondary aryl amine, or a combination thereof. In yet a further aspect, the hindered phenol comprises one or more compounds selected from triethylene glycol bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],
2.4- bis(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-l,3,5-triazine, pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thiodiethylene
bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl
3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N'-hexamethylene
bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), tetrakis(methylene
3.5- di-tert-butyl-hydroxycinnamate)methane, and octadecyl
3,5-di-tert-butylhydroxyhydrocinnamate. In an even further aspect, the hindered phenol comprises octadecyl-3 -(3 ,5 -di-t-butyl-4-hydroxyphenyl)-propionate .
[00123] In a further aspect, the secondary anti-oxidant is selected from an
organophosphate and thioester, or a combination thereof. In a still further aspect, the secondary anti-oxidant comprises one or more compounds selected from
tetrakis(2,4-di-tert-butylphenyl) [1,1 -biphenyl]-4,4'-diylbisphosphonite,
tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerytritoldiphosphite, tris(nonyl phenyl)phosphite, and distearyl pentaerythritol diphosphite. In yet a further aspect, the secondary anti-oxidant comprises tris(2,4-di-tert-butylphenyl) phosphite.
[00124] Antioxidants are generally used in amounts of about 0.01 wt% to about 3 wt%, optionally about 0.05 wt% to about 2.0 wt% of the blended thermoplastic composition.
[00125] In a further aspect, the primary antioxidant is present in an amount from about 0.01 wt% to about 3 wt%. In another aspect, the primary antioxidant is present in an amount from about 0.01 wt% to about 2.5 wt%. In still another aspect, the primary antioxidant is present in an amount from about 0.5 wt% to about 2.5 wt%. In yet a further aspect, the primary antioxidant is present in an amount from about 0.5 wt% to about 2.0 wt%. In still another aspect, the primary antioxidant is present in an amount from about 0.1 wt% to about 0.5 wt%. In still another aspect, the primary antioxidant is present in an amount from about 0.2 wt% to about 0.5 wt%. In still another aspect, the primary antioxidant is present in an amount from about 0.2 wt% to about 0.4 wt%.
[00126] In a further aspect, the secondary antioxidant is present in an amount from about 0.01 wt% to about 3.0 wt%. In another aspect, the secondary antioxidant is present in an amount from about 0.01 wt% to about 2.5 wt%. In still another aspect, the secondary antioxidant is present in an amount from about 0.5 wt% to about 2.5 wt%. In yet another aspect, the secondary antioxidant is present in an amount from about 0.5 wt% to about 2.0 wt%. In still another aspect, the secondary antioxidant is present in an amount from about 0.05 wt% to about 0.4 wt%. In still another aspect, the secondary antioxidant is present in an amount from about 0.05 wt% to about 0.2 wt%.
[00127] In various aspects, the disclosed polycarbonate blend compositions further comprise a hydrolytic stabilizer, wherein the hydrolytic stabilizer comprises a hydrotalcite and an inorganic buffer salt. In a further aspect, the disclosed polycarbonate blend composition comprises a hydrolytic stabilizer, wherein the hydrolytic stabilizer comprises one or more hydrotalcites and an inorganic buffer salt comprising one or more inorganic salts capable of pH buffering. Either synthetic hydrotalcites or natural hydrotalcites can be used as the hydrotalcite compound in the present invention. Exemplary hydrotalcites that are useful in the compositions of the present are commercially available and include, but are not limited to, magnesium hydrotalcites such as DHT-4C (available from Kyowa Chemical Co.); Hysafe 539 and Hysafe 530 (available from J.M. Huber Corporation).
[00128] In a further aspect, suitable thermal stabilizer additives include, for example, organic phosphites such as triphenyl phosphite, tris-(2,6-dimethylphenyl)phosphite, tris-(mixed mono-and di-nonylphenyl)phosphite or the like; phosphonates such as dimethylbenzene phosphonate or the like, organic phosphates such as trimethyl phosphate, thioesters such as pentaerythritol betalaurylthiopropionate, and the like, or combinations comprising at least one of the foregoing thermal stabilizers.
[00129] Thermal stabilizers are generally used in amounts of about 0.01 wt% to about 5 wt%, optionally about 0.05 wt% to about 2.0 wt% of the polycarbonate blend composition. In one aspect, the thermal stabilizer is present in an amount from about 0.01 wt% to about 3.0 wt%. In another aspect, the thermal stabilizer is present in an amount from about 0.01 wt% to about 2.5 wt%. In still another aspect, the thermal stabilizer is present in an amount from about 0.5 wt% to about 2.5 wt%. In still another aspect, the thermal stabilizer is present in an amount from about 0.5 wt% to about 2.0 wt%. In still another aspect, the thermal stabilizer is present in an amount from about 0.1 wt% to about 0.8 wt%. In still another aspect, the thermal stabilizer is present in an amount from about 0.1 wt% to about 0.7 wt%. In still another aspect, the thermal stabilizer is present in an amount from about 0.1 wt% to about 0.6 wt%. In still another aspect, the thermal stabilizer is present in an amount from about 0.1 wt% to about 0.5 wt%. In still another aspect, the thermal stabilizer is present in an amount from about 0.1 wt% to about 0.4 wt%. In still another aspect, the thermal stabilizer is present in an amount from about 0.05 wt% to about 1.0 wt%.
[00130] In various aspects, plasticizers, lubricants, and/or mold release agents additives can also be used. There is a considerable overlap among these types of materials, which include, for example, phthalic acid esters such as dioctyl-4,5-epoxy-hexahydrophthalate; tris(octoxycarbonylethyl)isocyanurate; tristearin; di- or polyfunctional aromatic phosphates such as resorcinol tetraphenyl diphosphate (RDP), the bis(diphenyl)phosphate of
hydroquinone and the bis(diphenyl)phosphate of bisphenol-A; poly-alpha-olefms; epoxidized soybean oil; silicones, including silicone oils; esters, for example, fatty acid esters such as alkyl stearyl esters, e.g. methyl stearate; stearyl stearate, pentaerythritol tetrastearate, and the like; mixtures of methyl stearate and hydrophilic and hydrophobic nonionic surfactants comprising polyethylene glycol polymers, polypropylene glycol polymers, and copolymers thereof; waxes such as beeswax, montan wax, paraffin wax or the like.
[00131] Blended thermoplastic composition additives such as plasticizers, lubricants, and/or mold release agents additive are generally used in amounts of about 0.01 wt% to about 20 wt%, optionally about 0.5 wt% to about 10 wt% the polycarbonate blend composition. In one aspect, the mold release agent is methyl stearate; stearyl stearate or pentaerythritol tetrastearate. In another aspect, the mold release agent is pentaerythritol tetrastearate.
[00132] In various aspects, the mold release agent is present in an amount from about 0.01 wt% to about 3.0 wt%. In another aspect, the mold release agent is present in an amount from about 0.01 wt% to about 2.5 wt%. In still another aspect, the mold release agent is present in an amount from about 0.5 wt% to about 2.5 wt%. In still another aspect, the mold release agent is present in an amount from about 0.5 wt% to about 2.0 wt%. In still another aspect, the mold release agent is present in an amount from about 0.1 wt% to about 0.6 wt%. In still another aspect, the mold release agent is present in an amount from about 0.1 wt% to about 0.5 wt%.
[00133] In a further aspect, the anti-drip agents can also be present. In a further aspect, the anti-drip agent is a styrene-acrylonitrile copolymer encapsulated polytetrafluoroethylene. Exemplary anti-drip agents can include a fibril forming or non- fibril forming fluoropolymer such as polytetrafluoroethylene (PTFE). The anti-drip agent can optionally be encapsulated by a rigid copolymer, for example styrene-acrylonitrile (SAN). PTFE encapsulated in SAN is known as TSAN. Encapsulated fluoropolymers can be made by polymerizing the encapsulating polymer in the presence of the fluoropolymer, for example, in an aqueous dispersion. TSAN can provide significant advantages over PTFE, in that TSAN can be more readily dispersed in the composition. A suitable TSAN can comprise, for example, about 50 wt % PTFE and about 50 wt % SAN, based on the total weight of the encapsulated
fluoropolymer. Alternatively, the fluoropolymer can be pre -blended in some manner with a second polymer, such as for, example, an aromatic polycarbonate resin or SAN to form an agglomerated material for use as an anti-drip agent. Either method can be used to produce an encapsulated fluoropolymer.
[00134] In a further aspect, the anti-drip agent is present in an amount from about 0.01 wt% to about 3 wt%. In a still further aspect, the anti-drip agent is present in an amount from about 0.01 wt% to about 2.5 wt%. In yet a further aspect, the anti-drip agent is present in an amount from about 0.5 wt% to about 2.0 wt%.
[00135] In various aspects, the polycarbonate blend compositions of the present invention can further comprise an acid or an acid salt. In one embodiment, the acid or acid salt is an inorganic acid or inorganic acid salt. In one embodiment, the acid is an acid including a phosphorous containing oxy-acid. In one embodiment, the phosphorous containing oxy-acid is a multi-protic phosphorus containing oxy-acid having the general formula:
HmP,On,
where m and n are each 2 or greater and t is 1 or greater. Examples of the acids of the foregoing formula include, but are not limited to, acids represented by the following formulas: H3PO4, H3PO3, and H3PO2. Other exemplary acids include phosphoric acid, phosphorous acid, hypophosphorous acid, hypophosphoric acid, phosphinic acid, phosphonic acid,
metaphosphoric acid, hexametaphosphoric acid, thiophosphoric acid, fluorophosphoric acid, difluorophosphoric acid, fluorophosphorous acid, difluorophosphorous acid,
fluorohypophosphorous acid, or fluorohypophosphoric acid. Alternatively, acids and acid salts, such as, for example, sulphuric acid, sulphites, mono zinc phosphate, mono calcium phosphate, sodium acid pyrophosphate, mono natrium phosphate, and the like, can be used. The acid or acid salt is selected so that it can be effectively combined with the mineral filler to produce a synergistic effect and a balance of properties, such as flow and impact, in the polycarbonate or polycarbonate blend. In a further aspect, the weight ratio of acid to mineral filler component, or acid:mineral filler component weight ratio, can be from about 0.001 to about 0.04. PROPERTIES OF THE POLYCARBONATE BLEND COMPOSITIONS
[00136] In at least one aspect, the composition has improved impact properties. The improved impact properties may be seen at low temperatures. The improved impact properties allow the composition to have reduced cracking upon impact.
[00137] In a further aspect, the molded parts have an average notched Izod energy at 23°C ranging from 700 to 900 J/m and a % ductility of 100% according to ASTM D256-2010, for the black blends, and ranging from 600 to 800 J/m and a % ductility of 100% according to ASTM D256-2010, for the white blends. In an even further aspect, the molded parts have an average notched Izod energy at -30 °C ranging from 600 to 800 J/m and a % ductility of 100% according to ASTM D256-2010, for the black blends, and ranging from 450 to 650 J/m °C and a % ductility of 100% according to ASTM D256-2010, for the white blends. In at least one aspect, the molded parts have an average notched Izod energy at -40 °C of 550 to 750 J/m and a % ductility of 100% according to ASTM D256-2010, for black blends. In at least one aspect, the molded parts have an average notched Izod energy at -40 °C of 450 to 650 J/m and a % ductility of 100% according to ASTM D256-2010, for white blends. In another aspect, the molded parts have an average notched Izod energy at -50 °C of 500 to 700 J/m and a % ductility of 100% according to ASTM D256-2010, for black blends. In at least one aspect, the molded parts have an average notched Izod energy at -50 °C of 150 to 600 J/m and a % ductility of 100% according to ASTM D256-2010, for white blends.
[00138] In one aspect, the molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod energy at -40 °C of 700 J/m or greater and a ductility of 100% according to ASTM D256-2010. In another aspect, the a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -30 °C of 650 J/m or greater and a % ductility of 100% according to ASTM D256-2010.
[00139] In a further aspect, the molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -40 °C of 500 J/m or greater and a % ductility of 100% according to ASTM D256-2010.
[00140] In a further aspect, the molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -50 °C of 500 J/m or greater and a % ductility of 80% according to ASTM D256-2010.
[00141] In at least one aspect, the composition has an average melt flow rate (MFR) of 7 or greater at 300 °C/1.2 kg. In at least one aspect, the composition has an average MFR ranging from 7 to 20 at 300 °C/1.2 kg. In a further aspect, the composition has an average MFR ranging from 7 to 15 at 300 °C/1.2 kg, for example ranging from 7 to 11 at 300 °C/1.2 kg-
[00142] In at least one aspect, when there is an absence of colorants in the composition, the percent light transmission ranges from 73 to 85% and the percent haze ranges from 2 to 12%, when the thickness is 3.2mm
[00143] In at least one aspect, the composition has a deep black color capability. The deep black color capability is shown by L* (D65 ilium, lOdeg, specular component included). The L* is measured using CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode. In one aspect, the deep black color capability, L*, is less than 27.0. In at least one aspect, the deep black color capability L* ranges from 1 to 27.0. In another aspect, the deep black color capability L* ranges from 10 to 27.0. In a further aspect, the deep black color capability L* ranges from 20 to 27.0. In a further aspect, the deep black color capability L* ranges from 10 to 20. In a still further aspect, the deep black color capability L* ranges from 25 to 29. In a yet further aspect, the deep black color capability L* ranges from 26 to 28.
[00144] In at least one aspect, the composition has a deep black color capability. The deep black color capability is shown by L* (D65 ilium, lOdeg, specular component included). The L* is measured using CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode. In one aspect, the deep black color capability, L*, is less than 28.0. In at least one aspect, the deep black color capability L* ranges from 1 to 28.0. In another aspect, the deep black color capability L* ranges from 10 to 28.0. In a further aspect, the deep black color capability L* ranges from 20 to 28.0. In one aspect, the deep black color capability L* ranges from 10 to 20. In a still further aspect, the deep black color capability L* ranges from 26 to 30. In a yet further aspect, the deep black color capability L* ranges from 27 to 29.
[00145] In at least one aspect, the composition has a bright white color capability. The bright white color capability is shown by L* (D65 ilium, lOdeg, specular component included). The L* is measured using CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode. In one aspect, the bright white color capability L* is greater than 97.0. In at least one aspect, the bright white color capability L* is greater than 98.0. In a further aspect, the bright white color capability L* ranges from 95 to 99. In an even further aspect, the bright white color capability L* ranges from 97 to 99. In a yet further aspect, the bright white color capability L* ranges from 97.0 to 98.5. METHODS OF MANUFACTURE
[00146] The polycarbonate blend compositions of the present invention can be blended with the aforementioned ingredients by a variety of methods involving intimate admixing of the materials with any additional additives desired in the formulation. Because of the availability of melt blending equipment in commercial polymer processing facilities, melt processing methods are generally preferred. Illustrative examples of equipment used in such melt processing methods include: co-rotating and counter-rotating extruders, single screw extruders, co-kneaders, disc-pack processors and various other types of extrusion equipment. The temperature of the melt in the present process is preferably minimized in order to avoid excessive degradation of the resins. It is often desirable to maintain the melt temperature between about 230 °C and about 350 °C in the molten resin composition, although higher temperatures can be used provided that the residence time of the resin in the processing equipment is kept short. In some embodiments the melt processed composition exits processing equipment such as an extruder through small exit holes in a die. The resulting strands of molten resin are cooled by passing the strands through a water bath. The cooled strands can be chopped into small pellets for packaging and further handling.
[00147] Compositions can be manufactured by various methods, including batch or continuous techniques that employ kneaders, extruders, mixers, and the like. For example, the composition can be formed as a melt blend employing a twin-screw extruder. In some embodiments at least some of the components are added sequentially. For example, the polycarbonate polymer, the first polysiloxane-polycarbonate component, the second polysiloxane-polycarbonate component, and the colorant composition can be added to the extruder at the feed throat or in feeding sections adjacent to the feed throat, or in feeding sections adjacent to the feed throat, while the various composition additives, e.g. antioxidants and/or a mold release agent, can be added to the extruder in a subsequent feeding section downstream. Alternatively, the sequential addition of the components may be accomplished through multiple extrusions. A composition may be made by preextrusion of selected components, such as the polycarbonate polymer, the first polysiloxane-polycarbonate component, the second polysiloxane-polycarbonate component, and the colorant composition to produce a pelletized mixture. A second extrusion can then be employed to combine the preextruded components with any remaining components. Additional composition additives, e.g. antioxidants and/or mold release agents, can be added as part of a masterbatch or directly. The composition additives can be added either at the feedthroat or downstream. The extruder can be a two lobe or three lobe twin screw extruder. [00148] In various aspects, the polycarbonate polymer, the first
polysiloxane-" polycarbonate component, the second polysiloxane-polycarbonate component, the colorant composition and/or other optional components are first blended in a
HENSCHEL-Mixer™ high speed mixer. Other low shear processes, including but not limited to hand mixing, can also accomplish this blending. The blend is then fed into the throat of a twin-screw extruder via a hopper. Alternatively, at least one of the components can be incorporated into the composition by feeding directly into the extruder at the throat and/or downstream through a sidestuffer. Additives can also be compounded into a masterbatch with a desired polymeric resin and fed into the extruder. The extruder is generally operated at a temperature higher than that necessary to cause the composition to flow. The extrudate is immediately quenched in a water batch and pelletized. The pellets, so prepared, can be one-fourth inch long or less as desired. Such pellets can be used for subsequent molding, shaping, or forming.
[00149] In various aspects, the invention relates to methods of preparing a composition, the method comprising the step of mixing a polycarbonate polymer, a first
polysiloxane-polycarbonate copolymer, a second polysiloxane-polycarbonate copolymer, and a colorant composition.
[00150] In one aspect, the invention relates to methods of a preparing a composition, comprising the step of mixing: (a) a polycarbonate homopolymer; (b) a first
polysiloxane-polycarbonate copolymer comprising: (i) poly diorganosiloxane blocks comprising repeating structural units of formula:
Figure imgf000042_0001
wherein the polydiorganosiloxane block length (E) is from 30 to 60; and (ii) polycarbonate blocks comprising polycarbonate units of formula:
Figure imgf000042_0002
wherein at least 60 percent of the total number of R groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the first polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 4 to 8 wt % diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer; (c) a second polysiloxane-polycarbonate copolymer comprising: (i)
polydiorganosiloxane blocks comprising repeating structural units of formula:
Figure imgf000043_0001
wherein the polydiorganosiloxane block length (E) is from 30 to 100; and (ii) polycarbonate blocks comprising polycarbonate units of formula:
O
R1— O C O wherein at least 60 percent of the total number of R1 groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the second polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 15 to 30 wt % diorganosiloxane based on the total weight of the second
polysiloxane-polycarbonate copolymer; and (d) a colorant composition; wherein the blend composition has an average melt flow rate (MFR) of 7 or greater measured at 300 °C/1.2 kg; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has a black color characterized by an average L* value of 27 or less as measured by the CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -30 °C of 650 J/m or greater and a % ductility of 100% according to ASTM D256-2010.
[00151] In one aspect, the invention relates to methods of a preparing a composition, comprising the step of mixing: (a) from 15 wt% to 30 wt% of a polycarbonate
homopolymer; (b) from 11 wt% to 29 wt% of a first polysiloxane-polycarbonate copolymer comprising: (i) polydiorganosiloxane blocks comprising repeating structural units of formula:
Figure imgf000044_0001
wherein the polydiorganosiloxane block length (E) is from 30 to 60; and (ii) polycarbonate blocks comprising polycarbonate units of formula:
Figure imgf000044_0002
wherein at least 60 percent of the total number of R1 groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the first polysiloxane -polycarbonate copolymer comprises a diorganosiloxane content of from 4 to 8 wt % diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer; (c) from greater than 0 wt% to 8 wt% of a second polysiloxane-polycarbonate copolymer comprising: (i) polydiorganosiloxane blocks comprising repeating structural units of formula:
Figure imgf000044_0003
wherein the polydiorganosiloxane block length (E) is from 30 to 100; and (ii) polycarbonate blocks comprising polycarbonate units of formula:
Figure imgf000044_0004
wherein at least 60 percent of the total number of R1 groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the second polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 15 to 30 wt % diorganosiloxane based on the total weight of the second
polysiloxane-polycarbonate copolymer; and (d) a colorant composition; wherein the total weight percent wherein the total weight percent is relative to the polycarbonate polymer, first polysiloxane -polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer blend composition has an average melt flow rate (MFR) of 7 or greater measured at
300 °C/1.2 kg; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has a black color characterized by an average L* value of 27 or less as measured by the CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -30 °C of 650 J/m or greater and a % ductility of 100% according to ASTM D256-2010.
[00152] In one aspect, the invention relates to methods of a preparing a composition, comprising the step of mixing: (a) from 15 wt% to 45 wt% of a polycarbonate
homopolymer; (b) from 50 wt% to 96 wt% of a first polysiloxane-polycarbonate copolymer comprising: (i) poly diorganosiloxane blocks comprising repeating structural units of formula:
Figure imgf000045_0001
wherein the polydiorganosiloxane block length (E) is from 30 to 60; and (ii) polycarbonate blocks comprising polycarbonate units of formula:
O
-R— O- c- o- wherein at least 60 percent of the total number of R1 groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the first polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 4 to 8 wt % diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer; (c) from greater than 0 wt% to 8 wt% of a second polysiloxane-polycarbonate copolymer comprising: (i) polydiorganosiloxane blocks comprising repeating structural units of formula:
Figure imgf000046_0001
E wherein the polydiorganosiloxane block length (E) is from 30 to 100; and (ii) polycarbonate blocks comprising polycarbonate units of formula:
Figure imgf000046_0002
wherein at least 60 percent of the total number of R groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the second polysiloxane -polycarbonate copolymer comprises a diorganosiloxane content of from 15 to 30 wt % diorganosiloxane based on the total weight of the second
polysiloxane -polycarbonate copolymer; and (d) a colorant composition; wherein the total weight percent wherein the total weight percent is relative to the polycarbonate polymer, first polysiloxane -polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer blend composition has an average melt flow rate (MFR) of 7 or greater measured at
300 °C/1.2 kg; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has a black color characterized by an average L* value of 27 or less as measured by the CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -30 °C of 650 J/m or greater and a % ductility of 100% according to ASTM D256-2010.
METHODS TO REDUCE CRACKING
[00153] The composition may be used as part of a method for reducing cracking because of its impact properties.
[00154] In at least one aspect, a method for reducing the rate of cracking of an electronic housing, the method comprising: a) providing the composition, disclosed above; b) molding said electronic housing; and c) applying stress to said housing.
[00155] In one aspect, the electronic housing may be housing for a cell phone or smart phone. In another aspect, a method of making a housing to reduce the rate of cracking, the method comprising: a) providing the composition, disclosed above; b) molding the composition, disclosed above; c) hard coating the composition with a hard coat that is less than or equal to 13 microns; and d) drilling one or more apertures in said molded housing.
[00156] The method may be used to prepare housing for a gaming system, a cell phone, a smart phone, a GPS device, a laptop computer, a tablet computer, an e- reader, a copier, a sports goggle, or an eyeglass frame.
[00157] The molding and the hard coating performed in the method may be done using standard techniques. The aperture drilling may be performed using standard techniques.
[00158] The reduced rate of cracking may be seen by the impact properties. For example, the improved impact strength may show a reduced rate of cracking. In other words, this relationship may be illustrated by the greater the impact strength, the smaller the rate of cracking. The impact strength may be shown by the average notched Izod energy, for example according to the ASTM D256-2010. The impact strength or properties may also be shown by other standard tests used to measure impact properties.
[00159] The hard coating may have a hard coat that is less than or equal to 13 microns. The hard coating may have a hard coat that is less than or equal to 10 microns. The hard coating may have a hard coat that is less than or equal to 7 microns.
[00160] Still further, the resulting composite mixture can be used to provide any desired shaped, formed, or molded articles. For example, the composite mixture may be molded into useful shaped articles by a variety of means such as injection molding, extrusion, rotational molding, blow molding and thermoforming. As noted above, the disclosed composites are particularly well suited for use in the manufacture of electronic components and devices. As such, according to some aspects, the disclosed composites can be used to form articles such as printed circuit board carriers, burn in test sockets, flex brackets for hard disk drives, and the like.
ARTICLES OF MANUFACTURE
[00161] The improved impact properties make the composition suitable for use in an article. For example, in various aspects, the present invention pertains to shaped, formed, or molded articles comprising the polycarbonate blend compositions. The polycarbonate blend compositions can be molded into useful shaped articles by a variety of means such as injection molding, extrusion, rotational molding, blow molding and thermoforming to form articles. The polycarbonate blend compositions described herein can also be made into film and sheet as well as components of laminate systems. In a further aspect, a method of manufacturing an article comprises melt blending the polycarbonate polymer, the first polysiloxane -polycarbonate component, the second polysiloxane -polycarbonate component, and the colorant composition; and molding the extruded composition into an article. In a still further aspect, the extruding is done with a twin-screw extruder.
[00162] In at least one aspect, the article is an injection molded article. In a further aspect, the article is an extruded film or sheet. The composition may be formed into the article, film, or sheet using conventional methods.
[00163] In at least one aspect, the article has a thickness less than 1.5 mm.
[00164] In an even further aspect, the article, film, or sheet may be used to form an apparatus. In a yet further aspect, the article may have one or more apertures.
[00165] In at least one aspect, the article is a component for an electronic device. In a further aspect, the electronic device is selected from a gaming system, a cell phone, a smart phone, a GPS device, a laptop computer, a tablet computer, an e- reader, a copier. In another aspect, the article is a component for a sports goggle or an eyeglass frame. For example, the article may be a component of a smart phone.
[00166] In various further aspects, formed articles include, for example, personal computers, notebook and portable computers, cell phone antennas and other such
communications equipment, medical applications, RFID applications, automotive
applications, and the like. In various further aspects, the article is a computer and business machine housing such as a housing for high end laptop personal computers, monitors, a hand held electronic device housing such as a housing for smart phones, tablets, music devices electrical connectors, and components of lighting fixtures, ornaments, home appliances, and the like.
[00167] In a further aspect, the present invention pertains to electrical or electronic devices comprising the disclosed polycarbonate blend compositions. In a further aspect, the electrical or electronic device comprising the disclosed polycarbonate blend compositions is a cellphone, a MP3 player, a computer, a laptop, a camera, a video recorder, an electronic tablet, a pager, a hand receiver, a video game, a calculator, a wireless car entry device, an automotive part, a filter housing, a luggage cart, an office chair, a kitchen appliance, an electrical housing, an electrical connector, a lighting fixture, a light emitting diode, an electrical part, or a telecommunications part.
[00168] In various aspects, the polymer composition can be used in the field of electronics. In a further aspect, non-limiting examples of fields which can use the disclosed blended thermoplastic polymer compositions include electrical, electro-mechanical, radio frequency (PvF) technology, telecommunication, automotive, aviation, medical, sensor, military, and security. In a still further aspect, the use of the disclosed blended thermoplastic polymer compositions can also be present in overlapping fields, for example in mechatronic systems that integrate mechanical and electrical properties which may, for example, be used in automotive or medical engineering.
EXAMPLES
[00169] The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the electrostatic dissipative composites disclosed and claimed herein can be made and evaluated, and are intended to be purely exemplary and are not intended to limit the disclosure. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in C or is at ambient temperature, and pressure is at or near atmospheric.
[00170] In the following example, the polycarbonate-siloxane copolymer blend composition was manufactured and tested. The raw materials used in the composition are shown in Table 1.
Table 1: Raw Material Description
Figure imgf000049_0001
Raw Material Description
PA2 Phosphorous acid; powder mixture of 0.62% of phosphorous
acid solution in water (45%) and 99.38%) of Bisphenol A polycarbonate.
CB Carbon Black (Pigment Black)
TD Titanium Dioxide, coated (Pigment White 6)
UV UV absorber from the benzotriazole class with the chemical
name 2-(2'-Hydroxy-5'-octylphenyl)-benzotriazol; available under the trade name CYASORB™ UV-5411.
PETS Release agent, pentaerythritoltetrastearate; available under the trade name Glycolube P (Lonza).
[00171] The tested polycarbonate-siloxane copolymer blend compositions are listed in Table 2a and Table 2b. Table 2a shows the compositions in solvent black color. Table 2b shows the compositions in bright white color. For every composition the siloxane percentage equals 4.98 w%, meaning that the siloxane percentage is held constant.
Additional solvent black compositions are described in Table 6 below.
Table 2a. Compositions in solvent black color in weight percentage.
Figure imgf000050_0001
^Organic colorant mixture consisting of 0.0309 Solvent Green 3,
0.0291 Solvent Red 52, 0.0001 Solvent Blue 104, and 0.0510
Solvent Yellow 93.
Table 2b. Compositions in bright white color in weight percentage.
Figure imgf000050_0002
^Organic colorant mixture consisting of 0.0162
2,2'-(l,2-ethenediyl)bis(4,l-phenylene)bisbenzoxazole, 0.00003
Pigment Blue 29, and 0.00002 Solvent Yellow 93.
Table 2c. Compositions in natural color (no pigments)
Figure imgf000051_0001
[00172] The compositions were compounded in a ZSK 30 mm co-rotating twin screw extruder using a melt temperature of 300 °C with a rate of 20 kgs/hr, and 20 inches of mercury vacuum and a screw speed of 400 RPM. The extrudate was cooled under water, pelletized and dried at 120 °C for four hours with a desiccant bed dryer. To make the test specimens, the dried pellets were injection molded using a Van Dorn 80T molding machine at 300 °C melt temperature to form test parts for impact and mechanical testing. Physical and mechanical properties of the test materials were measured using ASTM and ISO test standards.
[00173] A comparison of the physical properties between these materials is shown below in Table 3 and Table 4. Table 3 shows the impact data for the compositions in solvent black color. Table 4 shows the impact property data for the compositions in bright white color.
Table 3.
Figure imgf000051_0002
Measured on a molded part having a thickness of 3.2 mm formed from the indicated blend composition has a black color characterized by an averag value of 27 or less as measured by the CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode.
2 Measured in accordance with ASTM 1238 at a temperature of 300 °C under a 1.2 kg load. MFR values above are provided in gm/10 min.
3 Measured on a molded part having a thickness of 3.2 mm formed from the indicated blend composition has an average notched Izod impact (Nil) strength and ductility at the indicated temperature and determined in accordance with
ASTM D256-2010. The Nil strength values above are given in J/m and
ductility values are given in percent.
Table 4.
Figure imgf000052_0001
1 See Table 3 for description of tests, conditions of testing, and units associated with values.
Table 5.
Figure imgf000052_0002
[00174] The results listed in Table 3 show that the addition of PCI polycarbonate (BK-2) or 2.5 wt% PCPS2 (BK-3) result in modest improvement in low temperature impact energy and percent ductility. The addition of both PCI polycarbonate and 2.5 wt% PCPS2 (BK-4) shows 100% ductility at -40 °C and deep black color capability (L* < 27.0). the addition of 5.0 wt% PCPS2 shows 100% ductility at -50 °C but is not capable of deep black color (L* > 27.0). [00175] The results listed in Table 4 also show improvements in low temperature ductility. For example, 10 wt% PCPS2 and PCI in sample WH-5 shows 100% ductility at -50 °C. Further, samples WH-1 through WH-4 are capable of achieving bright white color
(L* >98.0).
Table 6. Compositions in solvent black color in weight percentage.
Figure imgf000053_0001
*OC colorant mixture consisting of 0.0510 Solvent Yellow 93,
0.0001 Solvent Blue 104, 0.0291 Solvent Red 52, and 0.0309
Solvent Green 7.
**Total siloxane loading from siloxane content of PCPS1 and
PCPS2.
Table 6. (continued).
Figure imgf000053_0002
[00176] A comparison of the physical properties for the compositions described above in Table 6 are shown below in Table 7. Table 7.
Figure imgf000054_0001
See Table 3 for description of tests, conditions of testing, and units associated with values except that melt volume rate (MVR) is used here, which was measured in accordance with ISO 1133 at a temperature of 300 °C under a 1.2 kg load at 360 second dwell and the values are provided in cm3/ 10 min.
Table 7. (continued).
Figure imgf000054_0002
[00177] The results listed in Table 7 show that compositions comprising about 4.0 wt% PCPS2 loading (BK-6 to BK-10) and at about 5.0 wt% PCPS2 loading (BK-11 to BK-14) have 80-100 % ductility at -30°C. Deep black colors (L* < 28.0) are only achieved at these PCPS2 loadings (4.0-5.0 wt%) when greater than about 50 wt% of PCPSl is present in the composition (BK-6, BK-7. BK-8, BK-11 and BK-12). In contrast, the compositions comprising less than about 50 wt% of PCPSl (BK-9, BK-10, BK-13 and BK-14) are not capable of achieving a deep black color (L* > 28.0).
[00178] Set forth below are some embodiments of the compositions and articles disclosed herein.
[00179] Embodiment 1 : A polycarbonate blend composition comprising: a polycarbonate polymer; a first polysiloxane-polycarbonate copolymer comprising:
i. polydiorganosiloxane blocks comprising repeating structural units of formula:
Figure imgf000055_0001
wherein the polydiorganosiloxane block length (E) is from 30 to 60; and polycarbonate blocks comprising polycarbonate units of formula:
Figure imgf000055_0002
wherein at least 60 percent of the total number of R1 groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties;
wherein the first polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 4 to 8 wt % diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer; b. a second polysiloxane-polycarbonate copolymer comprising: i. polydiorganosiloxane blocks comprising repeating structural units of formula:
Figure imgf000055_0003
wherein the polydiorganosiloxane block length (E) is from 30 to 100; and ii. polycarbonate blocks comprising polycarbonate units of formula:
O
R1— O C O wherein at least 60 percent of the total number of R1 groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the second polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 15 to 30 wt % diorganosiloxane based on the total weight of the second polysiloxane-polycarbonate copolymer; and c. a colorant composition; wherein the blend composition has an average melt flow rate (MFR) of 7 or greater measured at 300 °C/1.2 kg; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has a black color characterized by an average L* value of 27 or less as measured by the CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -30 °C of 650 J/m or greater and a % ductility of 100% according to ASTM D256-2010; and wherein R is the same or different, and is a C1-13 monovalent organic group; R2 is independently a divalent Ci-C30 organic group; M is independently a halogen, cyano, nitro, Ci-Cg alkylthio, Ci-Cg alkyl, Ci-Cg alkoxy, C2-Cg alkenyl, C2-Cg alkenyloxy group, C3-Cg cycloalkyl, C3-Cg cycloalkoxy, C6-Cio aryl, C6-Cio aryloxy, C7-C12 aralkyl, C7- C12 aralkoxy, C7- C12 alkylaryl, or C7- C12 alkylaryloxy, wherein each n is independently 0, 1, 2, 3, or 4.
[00180] Embodiment 2: The composition of Embodiment 1, wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod energy at -40 °C of 700 J/m or greater and a % ductility of 100% according to ASTM D256-2010.
[00181] Embodiment 3: The composition of Embodiments 1 or 2, wherein the colorant composition comprises less than 1.5 wt % of an inorganic colorant based on the total weight of the colorant composition.
[00182] Embodiment 4: The composition of any of Embodiments 1-3, wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod energy at -50 °C of 700 J/m or greater and a % ductility of 100% according to ASTM D256-2010.
[00183] Embodiment 5: The composition of any of Embodiments 1-4, wherein the second polysiloxane-polycarbonate copolymer is present in the blend composition in an amount of about 2.5 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
[00184] Embodiment 6: The composition of any of Embodiment 1-5, wherein the polycarbonate polymer is present in an amount in the range of from 15 wt% to 30 wt% relative to the total weight percent of the polycarbonate polymer, first
polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
[00185] Embodiment 7: The composition of any of Embodiment 1-5, wherein the polycarbonate polymer is present in an amount in the range of from 22 wt% to 29 wt% relative to the total weight percent of the polycarbonate polymer, first
polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
[00186] Embodiment 8: The composition of any of Embodiments 1-7, wherein the polycarbonate polymer comprises a blend of at least two polycarbonate polymers.
[00187] Embodiment 9: The composition of Embodiment 8, wherein the polycarbonate polymer comprises a first polycarbonate polymer and a second polycarbonate polymer.
[00188] Embodiment 10: The composition of Embodiment 9, wherein the first
polycarbonate polymer is a low flow polycarbonate.
[00189] Embodiment 11 : The composition of Embodiment 8 or 9, wherein the second polycarbonate polymer is a high flow polycarbonate.
[00190] Embodiment 12: The composition of Embodiment 9-11 , wherein the first polycarbonate polymer is present in an amount in the range of from 11 wt% to 29 wt% relative to the total weight percent of the polycarbonate polymer, first
polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer and wherein the second polycarbonate polymer is present in an amount in the range of from greater than 0 wt% to 8 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
[00191] Embodiment 13 : The composition of Embodiment 9-11 , wherein the first polycarbonate polymer is present in an amount in the range of from 14 wt% to 29 wt% relative to the total weight percent of the polycarbonate polymer, first
polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer and wherein the second polycarbonate polymer is present in an amount in the range of from greater than 0 wt% to 8 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
[00192] Embodiment 14: The composition of any of Embodiments 1-13, wherein the total combined weight percent of the first and second polysiloxane-polycarbonate copolymers present in the blend composition is in the range of from 70 wt% to 80 wt% relative to the total combined weight percent of the polycarbonate polymer, first
polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
[00193] Embodiment 15: The composition of any of Embodiments 1-14, wherein the first polysiloxane-polycarbonate copolymer is present in an amount in the range of from 65 wt% to 75 wt% relative to the total combined weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
[00194] Embodiment 16: The composition of any of Embodiments 1-15, wherein the second polysiloxane-polycarbonate copolymer is present in an amount in the range of from greater than 0 wt% to 5 wt% relative to the total combined weight percent of the
polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second
polysiloxane-polycarbonate copolymer.
[00195] Embodiment 17: The composition of any of Embodiments 1-16, wherein the total weight percentage of siloxane ranges from 4.5 wt % to 5.5 wt % based on the total combined weight of the first polysiloxane-polycarbonate, second polysiloxane-polycarbonate, and the polycarbonate.
[00196] Embodiment 18: The composition of any of Embodiments 1-17, wherein the absence of colorants, the percent light transmission ranges from 73 to 85% and the percent haze ranges from 2 to 12%, when the thickness is 3.2mm. Embodiment 19: A polycarbonate blend composition comprising:
a first polysiloxane-polycarbonate copolymer comprising: i. polydiorganosiloxane blocks comprising repeating structural units of formula:
Figure imgf000059_0001
wherein the polydiorganosiloxane block length (E) is from 30 to 60; and ii. polycarbonate blocks comprising polycarbonate units of formula:
Figure imgf000059_0002
wherein at least 60 percent of the total number of R1 groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the first polysiloxane-polycarbonate copolymer comprises a
diorganosiloxane content of from 4 to 8 wt % diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer; a second polysiloxane-polycarbonate copolymer comprising: i. polydiorganosiloxane blocks comprising repeating structural units of formula:
Figure imgf000059_0003
wherein the polydiorganosiloxane block length (E) is from 30 to 100; and ii. polycarbonate blocks comprising polycarbonate units of formula: O
R1— O C O wherein at least 60 percent of the total number of R1 groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the second polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 15 to 30 wt % diorganosiloxane based on the total weight of the second polysiloxane-polycarbonate copolymer; and f. a colorant composition; wherein the blend composition has an average melt flow rate (MFR) of 7 or greater measured at 300 °C/1.2 kg; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has a black color characterized by an average L* value of 28 or less as measured by the CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -30 °C of 600 J/m or greater and a % ductility of 80% according to ASTM D256-2010; and wherein R is the same or different, and is a C1-13 monovalent organic group; R2 is independently a divalent C1-C30 organic group; M is independently a halogen, cyano, nitro, Ci-Cg alkylthio, Ci-Cg alkyl, Ci-Cg alkoxy, C2-Cg alkenyl, C2-Cg alkenyloxy group, C3-C8 cycloalkyl, C3-C8 cycloalkoxy, C6-Ci0 aryl, C6-Ci0 aryloxy, C7-C12 aralkyl, C7- C12 aralkoxy, C7- C12 alkylaryl, or C7- C12 alkylaryloxy, wherein each n is independently 0, 1, 2, 3, or 4. Embodiment 20: A polycarbonate blend composition comprising:
g. a polycarbonate polymer; h. a first polysiloxane-polycarbonate copolymer comprising: i. polydiorganosiloxane blocks comprising repeating structural units of formula:
Figure imgf000061_0001
wherein the polydiorganosiloxane block length (E) is from 30 to 60; and ii. polycarbonate blocks comprising polycarbonate units of formula:
O
R— O C O- wherein at least 60 percent of the total number of R1 groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the first polysiloxane-polycarbonate copolymer comprises a
diorganosiloxane content of from 4 to 8 wt % diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer; a second polysiloxane-polycarbonate copolymer comprising: i. polydiorganosiloxane blocks comprising repeating structural units of formula:
Figure imgf000061_0002
wherein the polydiorganosiloxane block length (E) is from 30 to 100; and ii. polycarbonate blocks comprising polycarbonate units of formula: O
R1— O C O wherein at least 60 percent of the total number of R1 groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the second polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 15 to 30 wt % diorganosiloxane based on the total weight of the second polysiloxane-polycarbonate copolymer; and j. a colorant composition; wherein the blend composition has an average melt flow rate (MFR) of 7 or greater measured at 300 °C/1.2 kg; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has a black color characterized by an average L* value of 28 or less as measured by the CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -30 °C of 600 J/m or greater and a % ductility of 80% according to ASTM D256-2010; and wherein R is the same or different, and is a C1-13 monovalent organic group; R2 is independently a divalent C1-C30 organic group; M is independently a halogen, cyano, nitro, Ci-Cg alkylthio, Ci-Cg alkyl, Ci-Cg alkoxy, C2-Cg alkenyl, C2-Cg alkenyloxy group, C3-C8 cycloalkyl, C3-C8 cycloalkoxy, C6-Ci0 aryl, C6-Ci0 aryloxy, C7-C12 aralkyl, C7- C12 aralkoxy, C7- C12 alkylaryl, or C7- C12 alkylaryloxy, wherein each n is independently 0, 1, 2, 3, or 4.
[00199] Embodiment 21 : The composition of Embodiments 19 or 20, wherein the colorant composition comprises less than 12 wt % of an inorganic colorant based on the total weight of the colorant composition.
[00200] Embodiment 22: The composition of any of Embodiments 19-21 , wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod energy at -40 °C of 500 J/m or greater and a % ductility of 100% according to ASTM D256-2010.
[00201] Embodiment 23 : The composition of any of Embodiments 19-22, wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod energy at -50 °C of 500 J/m or greater and a % ductility of 80% according to ASTM D256-2010.
[00202] Embodiment 24: The composition of any of Embodiments 20-23, wherein the polycarbonate polymer is present in an amount in the range of from 0 wt% to 55 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
[00203] Embodiment 25 : The composition of any of Embodiments 20-24, wherein the polycarbonate polymer is present in an amount in the range of from 0 wt% to 45 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
[00204] Embodiment 26: The composition of any of Embodiments 20-25, wherein the polycarbonate polymer comprises a blend of at least two polycarbonate polymers.
[00205] Embodiment 27: The composition of Embodiment 26, wherein the
polycarbonate polymer comprises a first polycarbonate polymer and a second polycarbonate polymer.
[00206] Embodiment 28: The composition of Embodiment 27, wherein the first polycarbonate polymer is a low flow polycarbonate.
[00207] Embodiment 29: The composition of Embodiment 27 or 28, wherein the second polycarbonate polymer is a high flow polycarbonate.
[00208] Embodiment 30: The composition of any of Embodiments 27-29, wherein the first polycarbonate polymer is present in an amount in the range of from 10 wt% to 30 wt% relative to the total weight percent of the polycarbonate polymer, first
polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer and wherein the second polycarbonate polymer is present in an amount in the range of from greater than 0 wt% to 15 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second
polysiloxane-polycarbonate copolymer.
[00209] Embodiment 31 : The composition of any of Embodiments 19-30, wherein the total combined weight percent of the first and second polysiloxane-polycarbonate copolymers present in the blend composition is in the range of from 54 wt% to 100 wt% relative to the total combined weight percent of the polycarbonate polymer, first
polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
[00210] Embodiment 32: The composition of any of Embodiments 19-31, wherein the first polysiloxane-polycarbonate copolymer is present in an amount in the range of from 50 wt% to 95 wt% relative to the total combined weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
[00211] Embodiment 33: The composition of any of Embodiments 19-32, wherein the second polysiloxane-polycarbonate copolymer is present in an amount in the range of from greater than 0 wt% to 5 wt% relative to the total combined weight percent of the
polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second
polysiloxane-polycarbonate copolymer.
[00212] Embodiment 34: The composition of any of Embodiments 19-33, wherein the total weight percentage of siloxane ranges from 4.0 wt % to 7 wt % based on the total combined weight of the first polysiloxane-polycarbonate, second polysiloxane-polycarbonate, and the polycarbonate.
[00213] Embodiment 35: The composition of any of Embodiments 19-34, wherein the absence of colorants, the percent light transmission ranges from 65 to 85% and the percent haze ranges from 2 to 25%, when the thickness is 3.2 mm.
[00214] Embodiment 36: The composition of any of Embodiments 19-35, wherein the second polysiloxane-polycarbonate copolymer is present in the blend composition in an amount of about 4 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
[00215] Embodiment 37: The composition of any of Embodiments 1-36, wherein the second polysiloxane-polycarbonate copolymer is present in the blend composition in an amount less than 5 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer.
[00216] Embodiment 38: The composition of any of Embodiments 1-37, wherein the first polysiloxane-polycarbonate copolymer has an weight-averaged molecular weight, Mw, in the range of from 20,000 to 25,000 and wherein an injection molded part having a thickness of 3.2 mm formed from the blend composition has an average haze of less than 2.5 % measured according to ASTM D1003. [00217] Embodiment 39: The composition of any of Embodiments 1-38, wherein the second polysiloxane-polycarbonate copolymer has a weight-averaged molecular weight, Mw, in the range of from 25,000 to 35,000.
[00218] Embodiment 40: The composition of any of Embodiments 1-18 and 20-39, wherein the polycarbonate polymer is a Bisphenol-A -polycarbonate.
[00219] Embodiment 41 : The composition of Embodiment 40, wherein the Bisphenol-A polycarbonate has a weight-averaged molecular weight between 18,000 and 32,000.
[00220] Embodiment 42: The composition of Embodiment 40, wherein the Bisphenol-A polycarbonate has a weight-averaged molecular weight between 28,000 and 32,000.
[00221] Embodiment 43 : The composition of any of Embodiments 1-42, wherein the siloxane units of the first and second polysiloxane polycarbonate copolymers are
dimethylsiloxane units.
[00222] Embodiment 44: The composition of any of Embodiments 1-43, wherein the polydiorganosiloxane has moieties derived from eugenol, 4-allylphenol or 2-allylphenol.
[00223] Embodiment 45 : The composition of any of Embodiments 1-44, wherein the colorant composition comprises carbon black in an amount less than 1.5 wt % of the total colorant composition.
[00224] Embodiment 46: The composition of any of Embodiments 1-45, wherein the PDI of the first polysiloxane-polycarbonate and the second polysiloxane-polycarbonate ranges from 2 to 3.
[00225] Embodiment 47: The composition of any of Embodiments 1-46, wherein the first polysiloxane-polycarbonate and the second polysiloxane-polycarbonate comprise a polycarbonate unit derived from bisphenol-A.
[00226] Embodiment 48: An article of manufacture formed from the blend composition of any of Embodiments 1- 47.
[00227] Embodiment 49: The article of manufacture of Embodiment 48, wherein the thickness of the article is less than 1.5 mm.
[00228] Embodiment 50: The article of manufacture of Embodiment 48, wherein the thickness of the article is less than 1.5 mm in at least a portion of the article.
[00229] Embodiment 51 : The article of manufacture of any of Embodiments 48-50, wherein the article is an injection molded part.
[00230] Embodiment 52: The article of manufacture of any of Embodiments 48-50, wherein the article is an extruded film or sheet. [00231] Embodiment 53: The article of manufacture of any Embodiments 48-50, wherein the article is a component for an electronic device.
[00232] Embodiment 54: The article of manufacture of Embodiment 53, wherein the electronic device is selected from a gaming system, a cell phone, a smart phone, a GPS device, a laptop computer, a tablet computer, an e- reader, or a copier.
[00233] Embodiment 55: The article of manufacture of any of Embodiments 48-50, wherein the article is a component for a sports goggle or an eyeglass frame.
[00234] It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. Other aspects of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
[00235] The patentable scope of the invention is defined by the claims, and can include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

Claims

What is claimed is:
1 A polycarbonate blend composition comprising: a. ycarbonate polymer; b. a first polysiloxane-polycarbonate copolymer comprising: i. polydiorganosiloxane blocks comprising repeating structural units of formula:
Figure imgf000067_0001
wherein the polydiorganosiloxane block length (E) is from 30 to 60; and ii. polycarbonate blocks comprising polycarbonate units of formula:
O
R1— O C O wherein at least 60 percent of the total number of R1 groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the first polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 4 to 8 wt % diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer; c. a second polysiloxane-polycarbonate copolymer comprising: i. polydiorganosiloxane blocks comprising repeating structural units of formula:
Figure imgf000068_0001
E wherein the polydiorganosiloxane block length (E) is from 30 to 100; and polycarbonate blocks comprising polycarbonate units of formula:
Figure imgf000068_0002
wherein at least 60 percent of the total number of R groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the second polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 15 to 30 wt % diorganosiloxane based on the total weight of the second polysiloxane-polycarbonate copolymer; and d. a colorant composition; wherein the blend composition has an average melt flow rate (MFR) of 7 or greater measured at 300 °C/1.2 kg; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has a black color characterized by an average L* value of 27 or less as measured by the CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -30 °C of 650 J/m or greater and a % ductility of 100% according to ASTM D256-2010; and wherein R is the same or different, and is a C1-13 monovalent organic group; R2 is independently a divalent C1-C30 organic group; M is independently a halogen, cyano, nitro, Ci-Cg alkylthio, Ci-C8 alkyl, Ci-C8 alkoxy, C2-C8 alkenyl, C2-C8 alkenyloxy group, C3-C8 cycloalkyl, C3-C8 cycloalkoxy, C6-Cio aryl, C6-Cio aryloxy, C7-C12 aralkyl, C7- C12 aralkoxy, C7- C12 alkylaryl, or C7- C12 alkylaryloxy, wherein each n is independently 0, 1 , 2, 3, or 4. The composition of claim 1 , wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod energy at -40 °C of 700 J/m or greater and a % ductility of 100% according to ASTM D256-2010. The composition of claims 1 or 2, wherein the colorant composition comprises less than 1.5 wt % of an inorganic colorant based on the total weight of the colorant composition. The composition of any of claims 1-3, wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod energy at -50 °C of 700 J/m or greater and a % ductility of 100% according to ASTM D256-2010. The composition of any of claims 1-4, wherein the second polysiloxane -polycarbonate copolymer is present in the blend composition in an amount of about 2.5 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer. The composition of any of claim 1-5, wherein the polycarbonate polymer is present in an amount in the range of from 15 wt% to 30 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer. The composition of any of claim 1-5, wherein the polycarbonate polymer is present in an amount in the range of from 22 wt% to 29 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer. The composition of any of claims 1-7, wherein the polycarbonate polymer comprises a blend of at least two polycarbonate polymers. The composition of claim 8, wherein the polycarbonate polymer comprises a first polycarbonate polymer and a second polycarbonate polymer. The composition of claim 9, wherein the first polycarbonate polymer is a low flow polycarbonate. The composition of claim 8 or 9, wherein the second polycarbonate polymer is a high flow polycarbonate. The composition of claim 9-11, wherein the first polycarbonate polymer is present in an amount in the range of from 11 wt% to 29 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane -polycarbonate copolymer and wherein the second polycarbonate polymer is present in an amount in the range of from greater than 0 wt% to 8 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer. The composition of claim 9-11, wherein the first polycarbonate polymer is present in an amount in the range of from 14 wt% to 29 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer and wherein the second polycarbonate polymer is present in an amount in the range of from greater than 0 wt% to 8 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer. The composition of any of claims 1-13, wherein the total combined weight percent of the first and second polysiloxane-polycarbonate copolymers present in the blend composition is in the range of from 70 wt% to 80 wt% relative to the total combined weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer. The composition of any of claims 1-14, wherein the first polysiloxane-polycarbonate copolymer is present in an amount in the range of from 65 wt% to 75 wt% relative to the total combined weight percent of the polycarbonate polymer, first
polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer. The composition of any of claims 1-15, wherein the second polysiloxane-polycarbonate copolymer is present in an amount in the range of from greater than 0 wt% to 5 wt% relative to the total combined weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer. The composition of any of claims 1-16, wherein the total weight percentage of siloxane ranges from 4.5 wt % to 5.5 wt % based on the total combined weight of the first polysiloxane-polycarbonate, second polysiloxane-polycarbonate, and the polycarbonate. The composition of any of claims 1-17, wherein the absence of colorants, the percent light transmission ranges from 73 to 85% and the percent haze ranges from 2 to 12%, when the thickness is 3.2mm. A polycarbonate blend composition comprising: a. a first polysiloxane-polycarbonate copolymer comprising: i. polydiorganosiloxane blocks comprising repeating structural units of formula:
Figure imgf000071_0001
wherein the polydiorganosiloxane block length (E) is from 30 to 60; and ii. polycarbonate blocks comprising polycarbonate units of formula:
O
R1— O C O wherein at least 60 percent of the total number of R1 groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the first polysiloxane-polycarbonate copolymer comprises a
diorganosiloxane content of from 4 to 8 wt % diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer; b. a second polysiloxane-polycarbonate copolymer comprising: i. polydiorganosiloxane blocks comprising repeating structural units of formula:
Figure imgf000072_0001
wherein the polydiorganosiloxane block length (E) is from 30 to 100; and ii. polycarbonate blocks comprising polycarbonate units of formula:
O
R1— O C O wherein at least 60 percent of the total number of R1 groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the second polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 15 to 30 wt % diorganosiloxane based on the total weight of the second polysiloxane-polycarbonate copolymer; and c. a colorant composition; wherein the blend composition has an average melt flow rate (MFR) of 7 or greater measured at 300 °C/1.2 kg; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has a black color characterized by an average L* value of 28 or less as measured by the CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -30 °C of 600 J/m or greater and a % ductility of 80% according to ASTM D256-2010; and wherein R is the same or different, and is a C1-13 monovalent organic group; R2 is independently a divalent C1-C30 organic group; M is independently a halogen, cyano, nitro, Ci-Cg alkylthio, Ci-Cg alkyl, Ci-Cg alkoxy, C2-Cg alkenyl, C2-Cg alkenyloxy group, C3-C8 cycloalkyl, C3-C8 cycloalkoxy, C6-Ci0 aryl, C6-Ci0 aryloxy, C7-C12 aralkyl, C7- C12 aralkoxy, C7- C12 alkylaryl, or C7- C12 alkylaryloxy, wherein each n is independently 0, 1, 2, 3, or 4. A polycarbonate blend composition comprising: a. a polycarbonate polymer; b. a first polysiloxane-polycarbonate copolymer comprising: i. polydiorganosiloxane blocks comprising repeating structural units of formula:
Figure imgf000073_0001
wherein the polydiorganosiloxane block length (E) is from 30 to 60; and ii. polycarbonate blocks comprising polycarbonate units of formula:
O
R1— O C O wherein at least 60 percent of the total number of R1 groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the first polysiloxane-polycarbonate copolymer comprises a
diorganosiloxane content of from 4 to 8 wt % diorganosiloxane based on the total weight of the first polysiloxane-polycarbonate copolymer; c. a second polysiloxane-polycarbonate copolymer comprising: i. polydiorganosiloxane blocks comprising repeating structural units of formula:
Figure imgf000074_0001
E wherein the polydiorganosiloxane block length (E) is from 30 to 100; and polycarbonate blocks comprising polycarbonate units of formula:
Figure imgf000074_0002
wherein at least 60 percent of the total number of R groups comprise aromatic moieties and the balance thereof comprise aliphatic, alicyclic, or aromatic moieties; wherein the second polysiloxane-polycarbonate copolymer comprises a diorganosiloxane content of from 15 to 30 wt % diorganosiloxane based on the total weight of the second polysiloxane-polycarbonate copolymer; and d. a colorant composition; wherein the blend composition has an average melt flow rate (MFR) of 7 or greater measured at 300 °C/1.2 kg; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has a black color characterized by an average L* value of 28 or less as measured by the CIE Lab method, 10 degree observer, D65 illuminant, specular component included, measured in reflectance mode; and wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod impact energy at -30 °C of 600 J/m or greater and a % ductility of 80% according to ASTM D256-2010; and wherein R is the same or different, and is a C1-13 monovalent organic group; R2 is independently a divalent C1-C30 organic group; M is independently a halogen, cyano, nitro, Ci-Cg alkylthio, Ci-Cg alkyl, Ci-Cg alkoxy, C2-C8 alkenyl, C2-C8 alkenyloxy group, C3-C8 cycloalkyl, C3-C8 cycloalkoxy, C6-Ci0 aryl, C6-Ci0 aryloxy, C7-C12 aralkyl, C7- C12 aralkoxy, C7- C12 alkylaryl, or C7- C12 alkylaryloxy, wherein each n is independently 0, 1 , 2, 3, or 4. The composition of claims 19 or 20, wherein the colorant composition comprises less than 12 wt % of an inorganic colorant based on the total weight of the colorant composition. The composition of any of claims 19-21 , wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod energy at -40 °C of 500 J/m or greater and a % ductility of 100% according to ASTM D256-2010. The composition of any of claims 19-22, wherein a molded part having a thickness of 3.2 mm formed from the blend composition has an average notched Izod energy at -50 °C of 500 J/m or greater and a % ductility of 80% according to ASTM D256-2010. The composition of any of claims 20-23, wherein the polycarbonate polymer is present in an amount in the range of from 0 wt% to 55 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane -polycarbonate copolymer. The composition of any of claims 20-24, wherein the polycarbonate polymer is present in an amount in the range of from 0 wt% to 45 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer. The composition of any of claims 20-25, wherein the polycarbonate polymer comprises a blend of at least two polycarbonate polymers. The composition of claim 26, wherein the polycarbonate polymer comprises a first polycarbonate polymer and a second polycarbonate polymer. The composition of claim 27, wherein the first polycarbonate polymer is a low flow polycarbonate. The composition of claim 27 or 28, wherein the second polycarbonate polymer is a high flow polycarbonate. The composition of any of claims 27-29, wherein the first polycarbonate polymer is present in an amount in the range of from 10 wt% to 30 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer and wherein the second polycarbonate polymer is present in an amount in the range of from greater than 0 wt% to 15 wt% relative to the total weight percent of the polycarbonate polymer, first
polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer. The composition of any of claims 19-30, wherein the total combined weight percent of the first and second polysiloxane-polycarbonate copolymers present in the blend composition is in the range of from 54 wt% to 100 wt% relative to the total combined weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer. The composition of any of claims 19-31, wherein the first polysiloxane-polycarbonate copolymer is present in an amount in the range of from 50 wt% to 95 wt% relative to the total combined weight percent of the polycarbonate polymer, first
polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer. The composition of any of claims 19-32, wherein the second polysiloxane-polycarbonate copolymer is present in an amount in the range of from greater than 0 wt% to 5 wt% relative to the total combined weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer. The composition of any of claims 19-33, wherein the total weight percentage of siloxane ranges from 4.0 wt % to 7 wt % based on the total combined weight of the first
polysiloxane-polycarbonate, second polysiloxane-polycarbonate, and the polycarbonate. The composition of any of claims 19-34, wherein the absence of colorants, the percent light transmission ranges from 65 to 85% and the percent haze ranges from 2 to 25%, when the thickness is 3.2 mm. The composition of any of claims 19-35, wherein the second polysiloxane-polycarbonate copolymer is present in the blend composition in an amount of about 4 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer. The composition of any of claims 1-36, wherein the second polysiloxane-polycarbonate copolymer is present in the blend composition in an amount less than 5 wt% relative to the total weight percent of the polycarbonate polymer, first polysiloxane-polycarbonate copolymer, and second polysiloxane-polycarbonate copolymer. The composition of any of claims 1-37, wherein the first polysiloxane-polycarbonate copolymer has an weight-averaged molecular weight, Mw, in the range of from 20,000 to 25,000 and wherein an injection molded part having a thickness of 3.2 mm formed from the blend composition has an average haze of less than 2.5 % measured according to ASTM D1003. The composition of any of claims 1-38, wherein the second polysiloxane-polycarbonate copolymer has a weight-averaged molecular weight, Mw, in the range of from 25,000 to 35,000. The composition of any of claims 1-18 and 20-39, wherein the polycarbonate polymer is a Bisphenol-A -polycarbonate. The composition of claim 40, wherein the Bisphenol-A polycarbonate has a
weight-averaged molecular weight between 18,000 and 32,000. The composition of claim 40, wherein the Bisphenol-A polycarbonate has a
weight-averaged molecular weight between 28,000 and 32,000. The composition of any of claims 1-42, wherein the siloxane units of the first and second polysiloxane polycarbonate copolymers are dimethylsiloxane units. The composition of any of claims 1-43, wherein the polydiorganosiloxane has moieties derived from eugenol, 4-allylphenol or 2-allylphenol. The composition of any of claims 1-44, wherein the colorant composition comprises carbon black in an amount less than 1.5 wt % of the total colorant composition. The composition of any of claims 1-45, wherein the PDI of the first
polysiloxane-polycarbonate and the second polysiloxane-polycarbonate ranges from 2 to 3. The composition of any of claims 1-46, wherein the first polysiloxane-polycarbonate and the second polysiloxane-polycarbonate comprise a polycarbonate unit derived from bisphenol-A. An article of manufacture formed from the blend composition of any of claims 1-47. The article of manufacture of claim 48, wherein the thickness of the article is less than 1.5 mm. The article of manufacture of claim 48, wherein the thickness of the article is less than 1.5 mm in at least a portion of the article. The article of manufacture of any of claims 48-50, wherein the article is an injection molded part. The article of manufacture of any of claims 48-50, wherein the article is an extruded film or sheet. The article of manufacture of any claims 48-50, wherein the article is a component for an electronic device. The article of manufacture of claim 53, wherein the electronic device is selected from a gaming system, a cell phone, a smart phone, a GPS device, a laptop computer, a tablet computer, an e- reader, or a copier. The article of manufacture of any of claims 48-50, wherein the article is a component for a sports goggle or an eyeglass frame.
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US9708447B2 (en) 2012-12-20 2017-07-18 Sabic Global Technologies B.V. Blends containing photoactive additive
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US9688855B2 (en) 2015-11-17 2017-06-27 Sabic Global Technologies B.V. Polycarbonate-polysiloxane copolymer compositions for mobile phone housing applications
US9598577B1 (en) 2015-11-17 2017-03-21 Sabic Global Technologies B.V. Polycarbonate-polysiloxane copolymer compositions, articles formed therefrom, and methods of manufacture thereof
US9598578B1 (en) 2015-11-17 2017-03-21 SABIC Global Technologies B.V Polycarbonate-polysiloxane copolymer compositions, articles formed therefrom, and methods of manufacture thereof
US20180362758A1 (en) * 2015-12-21 2018-12-20 Sabic Global Technologies B.V. Thermoplastic compositions for laser direct structuring and methods for the manufacture and use thereof
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CN104583320B (en) 2016-06-22
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KR101572068B1 (en) 2015-11-26
CN104583320A (en) 2015-04-29
EP2890743A4 (en) 2015-08-26
EP2890743A1 (en) 2015-07-08
US9587109B2 (en) 2017-03-07
EP2890743B1 (en) 2017-07-26

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